Source reagent compositions and method for forming metal films on a substrate by chemical vapor deposition

ABSTRACT

A metalorganic complex composition comprising a metalorganic complex selected from the group consisting of: metalorganic complexes comprising one or more metal central atoms coordinated to one or more monodentate or multidentate organic ligands, and complexed with one or more complexing monodentate or multidentate ligands containing one or more atoms independently selected from the group consisting of atoms of the elements C, N, H, S, O and F; wherein when the number of metal atoms is one and concurrently the number of complexing monodentate or multidentate ligands is one, then the complexing monodentate or multidentate ligand of the metalorganic complex is selected from the group consisting of beta-ketoiminates, beta-diiminates, C 2 -C 10  alkenyl, C 2 -C 15  cycloalkenyl and C 6 -C 10  aryl.

CROSS-REFERENCE TO RELATED APPLICATIONS

This is a continuation of U.S. patent application Ser. No. 09/649,549filed Aug. 28, 2000 (now allowed) in the names of Robin A. Gardiner, etal., which in turn is a continuation-in-part of U.S. patent applicationSer. No. 08/484,654 filed Jun. 7, 1995 (now U.S. Pat. No. 6,110,529) inthe names of Robin A. Gardiner, et al., which in turn is acontinuation-in-part of U.S. patent application Ser. No. 08/414,504filed Mar. 31, 1995 (now U.S. Pat. No. 5,820,664), in the names of RobinA. Gardiner, et al., which in turn is a continuation-in-part of U.S.patent application Ser. No. 08/280,143 filed Jul. 25, 1994 (now U.S.Pat. No. 5,536,323) in the names of Peter S. Kirlin, et al., which inturn is a continuation of U.S. patent application Ser. No. 07/927,134filed Aug. 7, 1992 (now abandoned) in the names of Peter S. Kirlin, etal., which in turn is a continuation-in-part of U.S. patent applicationSer. No. 07/807,807 filed Dec. 31, 1991 (now U.S. Pat. No. 5,204,314) inthe names of Peter S. Kirlin, et al., which in turn is a continuation ofU.S. patent application Ser. No. 07/549,389 filed Jul. 6, 1990 (nowabandoned) in the names of Peter S. Kirlin, et al. U.S. patentapplication Ser. No. 08/484,654 filed Jun. 7, 1995 (now U.S. Pat. No.6,110,529) in the names of Robin A. Gardiner, et al., is also acontinuation-in-part of U.S. patent application Ser. No. 08/181,800filed Jan. 15, 1994 (now U.S. Pat. No. 5,453,494) in the names of PeterS. Kirlin, et al., which in turn is a continuation-in-part of U.S.patent application Ser. No. 07/918,141 filed Jul. 22, 1992 (now U.S.Pat. No. 5,280,012) in the names of Peter S. Kirlin, et al., which inturn is a continuation of U.S. patent application Ser. No. 07/615,303filed Nov. 19, 1990 (now abandoned) in the names of Peter S. Kirlin, etal., which in turn is a division of U.S. patent application Ser. No.07/581,631 filed Sep. 12, 1990 (now U.S. Pat. No. 5,225,561) in thenames of Peter S. Kirlin, et al., which in turn is acontinuation-in-part of U.S. patent application Ser. No. 07/549,389filed Jul. 6, 1990 (now abandoned) in the names of Peter S. Kirlin, etal.

GOVERNMENT RIGHTS IN THE INVENTION

This invention was made with Government support under Contract No.DNA001-92-C-0136 awarded by the U.S. Ballistic Missile DefenseOrganization (BMDO). The Government has certain rights in thisinvention.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention generally relates to precursor source reagentmetal-organic compositions, a chemical vapor deposition (CVD) processutilizing such precursor source reagent metal-organic compositions forformation of metal films on substrates, and to CVD processes utilizingliquid delivery and volatilization of such precursor source reagentmetal-organic compositions for supplying a source reagent vapor to a CVDreactor.

2. Description of the Related Art

Chemical vapor deposition is widely used for the formation of metalfilms on a variety of substrates. CVD is a particularly attractivemethod for forming metal films because it is readily scaled up toproduction runs and because the electronics industry has a wideexperience and an established equipment base in the use of CVDtechnology which can be applied to CVD processes.

CVD requires source reagents that are sufficiently volatile to permittheir gas phase transport into the decomposition reactor. The sourcereagent must decompose in the CVD reactor to deposit only the desiredelement(s) at the desired growth temperature on the substrate. Prematuregas phase reactions are desirably avoided, and it generally is desiredto controllably deliver source reagents into the CVD reactor to effectcorrespondingly close control of stoichiometry.

Many potentially useful metals do not form compounds which are wellsuited for CVD. Although some source reagents are solids which areamenable to sublimation for gas-phase transport into the CVD reactor,the sublimation temperature may be very close to decompositiontemperature. Accordingly, the reagent may begin to decompose in thelines leading to the CVD reactor, and it then becomes difficult tocontrol the stoichiometry of the deposited films.

Accordingly, there is a continuing search in the art for improved sourcereagent compositions which are amenable to vaporization to form thesource component vapor for CVD processes.

U.S. Pat. No. 5,204,314 discloses a process for supplying an involatilesource reagent in vapor form for CVD, in which reagent source liquid isflash vaporized on a high surface-to-volume ratio structure, followingwhich the vaporized reagent is flowed to the CVD reactor, for depositionof the desired metal or other component on the target substrate in thereactor.

In the chemical vapor deposition of multicomponent material systems,multiple source reagents are delivered to the CVD reactor. Aparticularly advantageous way of delivering multiple source reagents isto accurately mix neat liquid source reagents or liquid solutions ofsource reagents and then flash vaporize the mixture and deliver theresulting vapor to the reactor. It is possible in this situation for thereagents to undergo reactions, either in the liquid phase beforevaporization or in the gas phase after vaporization. If these reactionsconvert a source reagent to an insoluble or non-volatile product, or toa material of different chemical or physical properties, then theelements contained in that product will not reach the substrate and thestoichiometry of the deposited film will be incorrect.

Examples of this problem (wherein Et is ethyl; tBu is tert-butyl; iPr isisopropyl; and thd is tetramethylheptanedionate) include the following:

-   -   (i) during deposition of PbZr_(x)Ti_(1-x)O₃, using (Et)₄Pb,        Zr(OtBu)₄, and Ti(OiPr)₄ source reagents, ligand exchange        between the Zr and Ti reagents resulted in formation of        Zr(OiPr)₄ (and perhaps other products of which Zr(OiPr)₄ is a        monomer), which had very low volatility and which condensed in        the gas manifold or vaporizer;    -   (ii) when solutions of Ba(thd)₂ and Ti(OiPr)₄ were mixed prior        to vaporization, an insoluble precipitate was formed, presumably        Ba(OiPr)₂; and    -   (iii) when solutions of Pb(thd)₂ and Ti(OiPr)₄ were mixed in        butyl acetate, the reagents reacted to form compounds of        differing physical properties, such as Pb(OiPr)₂ and        Ti(OiPr)₂(thd)₂.

Another specific example illustrating this problem is the preparation offilms of strontium bismuth tantalate and strontium bismuth niobate(SrBi₂Ta₂O₉ and SrBi₂Nb₂O₉) by CVD for use in non-volatile ferroelectricrandom access memories. The most commonly used strontium source reagentsare β-diketonate complexes such as Sr(thd)₂. When a solution is heatedcontaining the following source reagents for deposition of SrBi₂Ta₂O₉:

-   -   Sr(thd)₂; Ta(OEt)₅; and Bi(Ph)₃ wherein Ph=phenyl,        the ethoxide ligands of the tantalum reagent exchange with the        thd ligands of the strontium reagent, leading to the formation        of undesirable strontium alkoxide species that have reduced        volatility and that can decompose in the vaporization zone.        Alternatively, when these reagents are provided separately in        bubblers, similar ligand exchange reactions occur in the gas        phase; the resulting solids constrict the gas lines or alter the        film stoichiometry.

In certain instances, such problems can be avoided by using identicalligands on the metals to make ligand exchange a degenerate reaction(i.e., where the exchanging ligand is identical to the original ligand).Examples of this approach include the use of tetraethylorthosilicate,triethylborate and triethylphosphite for deposition ofborophosphosilicate glasses (J. Electrochem. Soc., 1987, 134(2), 430).In many instances, however, this method for avoiding the problem is notpossible because the appropriate compound does not exist, is toounstable or involatile to be used for CVD, or otherwise hasdisadvantageous physicochemical material properties. For example, fordeposition of PbZr_(x)Ti_(1-x)O₃, a reagent system with identicalligands is problematic because while Pb(thd)₂ and Zr(thd)₄ are stableand volatile, Ti(thd)₄ does not exist and Ti(thd)₃ is extremely airsensitive. Similarly, while Ti(OtBu)₄ and Zr(OtBu)₄ are stable andvolatile, Pb(OtBu)₂ is thermally unstable at temperatures required forvolatilization.

The foregoing problems are also encountered in the circumstance wherethe metal source reagent is provided in a liquid solution and thesolvent contains moieties which react with ligands of the source reagentcompound to produce undesirable ligand exchange reaction by-productswhich display different physical properties and are involatile orinsoluble.

Accordingly, it is an object of the present invention to provide a CVDprocess utilizing improved metal source reagent compositions for thedeposition of corresponding metals and metal oxides.

It is another object of the invention to provide a CVD process utilizingimproved metal source reagent compositions in liquid or solution form,to simultaneously deliver the constituent metal(s) to a deposition locussuch as a chemical vapor deposition chamber.

It is a further object of the present invention to provide a CVD processutilizing liquid compositions of such type which are resistant todeleterious ligand exchange reactions.

It is yet another object of the invention to provide a liquid deliveryand chemical vapor deposition process in which precursor source reagentcompositions are volatilized and the resulting vapor is transported tothe CVD reactor for deposition of the desired component(s) on asubstrate disposed in the reactor.

Other objects and advantages of the invention will be more fullyapparent from the ensuing disclosure and appended claims.

SUMMARY OF THE INVENTION

The present invention generally relates to a method of forming on asubstrate a metal film, comprising depositing the metal film on thesubstrate via chemical vapor deposition from a metalorganic complex ofthe formula:

MA_(Y)X

wherein:M is a y-valent metal;A is a monodentate or multidentate organic ligandcoordinated to M which allows complexing of MA_(y) with X;y is an integer having a value of 2, 3 or 4;each of the A ligands may be the same or different; andX is a monodentate or multidentate ligand coordinated to Mand containing one or more atoms independently selected fromthe group consisting of atoms of the elements C, N, H, S, O and F.

In such method, M may for example be selected from the group consistingof Cu, Ba, Sr, La, Nd, Ce, Pr, Sm, Eu, Th, Gd, Tb, Dy, Ho, Er, Tm, Yb,Lu, Bi, Tl, Y, Pb, Ni, Pd, Pt, Al, Ga, In, Ag, Au, Co, Rh, Ir, Fe, Ru,Sn, Li, Na, K, Rb, Cs, Ca, Mg, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, and W. Theligand A may be selected from the group consisting of β-diketonates,cyclopentadienyls, alkyls, perfluoroalkyls, alkoxides,perfluoroalkoxides, and Schiff bases. Specific examples of A include:

(i) 2,2,6,6-tetramethyl-3,5-heptanedionate;(ii) 1,1,1,5,5,5-hexafluoro-2,4-pentanedionate;(iii) 1,1,1,2,2,3,3-heptafluoro-7,7-dimethyl-4,6-octanedionate;(iv) cyclopentadienyl;(v) 4,4′-(ethane-1,2-diyldiimino) bis(3-pentene-2-one);(vi) pentamethylcyclopentadienyl and other substitutedcyclopentadienyls;(vii) 2,4-pentanedionate; and(viii) 1,1,1-trifluoro-2,4-pentanedionate.

The ligand X in such complexes may, for example, be selected from thegroup consisting of:

-   -   (i) oxyhydrocarbyl ligands;    -   (ii) nitrogenous oxyhydrocarbyl ligands;    -   (iii) fluorooxyhydrocarbyl ligands; and    -   (iv) thiooxyhydrocarbyl ligands.

Specific classes of X ligand species include:

-   -   (a) amines and polyamines;    -   (b) bipyridines;    -   (c) ligands of the formula:

-   -   -   wherein G is —O—, —S—, or —NR—, wherein R is H or            hydrocarbyl;

    -   (d) crown ethers;

    -   (e) thioethers; and

    -   (f) ligands of the formula:

R⁰(C(R¹)₂C(R²)₂O)_(n)R⁰

-   -   -   wherein:            -   R⁰=H, methyl, ethyl, n-propyl, cyanato, perfluoroethyl,                perfluoro-n-propyl, or vinyl;            -   R¹═H, F, or a sterically acceptable hydrocarbyl                substituent;            -   R²═H, F, or a sterically acceptable hydrocarbyl                substituent;            -   n=2, 3, 4, 5, or 6; and            -   each R⁰, R¹, and R² may be the same as or different from                the other R⁰, R¹, and R², respectively.

Examples of such ligand X include tetraglyme, tetrahydrofuran,bipydridine, and 18-crown-6 ethers.

-   -   In a more specific aspect, the ligand X may have the formula:

R⁰(C(R¹)₂(R²)₂O)_(n)R⁰

-   -   wherein:        -   R⁰=H, methyl, ethyl, n-propyl, cyanato, perfluoroethyl,            perfluoro-n-propyl, or vinyl;        -   R¹=H, F, or a sterically acceptable hydrocarbyl substituent;        -   R²=H, F, or a sterically acceptable hydrocarbyl substituent;        -   n=2, 3, 4, 5, or 6; and        -   each R⁰, R¹, and R² may be the same as or different from the            other R⁰, R¹, and R², respectively.    -   In another specific aspect, the ligand X may have the formula:

R⁰O(C(R¹)₂C(R²)₂O)₄R⁰

-   -   wherein:    -   each R⁰, R¹, and R² is selected independently, and    -   R⁰=H, CH₃, or C₂H₅;    -   R¹ and R²=H or F.

In the metalorganic complexes described above, each of the ligands A maybe a constituent moiety of a single group which is coordinatinglyattached to M thereby. Alternatively, the ligand X and at least one ofthe ligands A may be a constituent moiety of a single group which iscoordinatingly attached to M thereby.

The method of the invention may therefore include the steps of:

providing the metalorganic complex in a solvent or suspending agenttherefor, as a metal source reagent solution comprising the metalorganiccomplex and the solvent or suspending agent,

-   -   volatilizing the metal source reagent liquid solution to yield a        metal source vapor, and    -   contacting the metal source vapor with the substrate, to deposit        the metal-containing film thereon.

In another aspect, the invention relates to a method of forming on asubstrate a metal film, comprising depositing the metal film on thesubstrate via chemical vapor deposition from a metalorganic compositioncomprising:

-   -   (i) a metalorganic complex of the formula:

MA_(Y)X

-   -   wherein:    -   M is a y-valent metal;    -   A is a monodentate or multidentate organic ligand coordinated to        M which allows complexing of MA_(y) with X;    -   y is an integer having a value of 2, 3 or 4;    -   each of the A ligands may be the same or different; and    -   X is a monodentate or multidentate ligand coordinated to M and        containing one or more atoms independently selected from the        group consisting of atoms of the elements C, N, H, S, O and F,    -   or precursor(s) or components thereof; and    -   (ii) a solvent or suspending agent therefor.

In such method, the metalorganic composition is suitably volatized toyield a metal source vapor, and the resulting metal source vapor iscontacted with the substrate, to deposit the metal-containing filmthereon. The composition may comprise the components of the metalorganiccomplex in a solvent, wherein the components react in situ in thesolvent to form the metalorganic complex. In like manner, thecomposition may comprise precursors of the metalorganic complex in thesolvent, wherein the precursors react in situ in the solvent to form themetalorganic complex.

In another aspect, the invention relates to a method of forming a metalfilm on a substrate, comprising depositing the metal film on thesubstrate via chemical vapor deposition from a metalorganic complex ofthe formula:

M₁M₂A_(y)X

wherein:M₁ is a metal of valence n;M₂ is a metal of valence y−n;M₁ and M₂ are different from one another;A is a monodentate or multidentate organic ligand coordinated to atleast one of M₁ andM₂ which allows complexing of M₁M₂A_(y) with X;n is an integer having a value of 1, 2 or 3;y is an integer having a value of 2, 3 or 4, and y>n;each of the A ligands may be the same or different; andX is a monodentate or multidentate ligand coordinated to at least one ofM₁ and M₂ and containing one or more atoms independently selected fromthe group consisting of atoms of the elements C, N, H, S, O and F.

Each of M₁ and M₂ in the metalorganic complex may be independentlyselected from the group consisting of Cu, Ba, Sr, La, Nd, Ce, Pr, Sm,Eu, Th, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Bi, Tl, Y, Pb, Ni, Pd, Pt, Al,Ga, In, Ag, Au, Co, Rh, Ir, Fe, Ru, Sn, Li, Na, K, Rb, Cs, Ca, Mg, Ti,Zr, Hf, V, Nb, Ta, Cr, Mo, and W.

In a preferred aspect, M₁ and M₂ are selected from the group of M₁/M₂pairs consisting of:

M₁ M₂ (i) Cu Sn; (ii) Cu In; (iii) Al Cu; (iv) Fe Mn; (v) Fe Ni; and(vi) Fe Co.

Still another method aspect of the invention relates to a method offorming a metal-containing film on a substrate, including providing ametal source reagent solution comprising a metal source reagent andsolvent medium, volatilizing the metal source reagent liquid solution toyield a metal source vapor, and contacting the metal source vapor withthe substrate, to deposit the metal-containing film thereon, wherein themetal source reagent solution comprises:

-   -   (i) at least one metal coordination complex including a metal to        which is coordinatively bound at least one ligand in a stable        complex, wherein the ligand is selected from the group        consisting of: β-diketonates, β-thioketonates, β-ketoiminates,        β-diiminates, C₁-C₈ alkyl, C₂-C₁₀ alkenyl, C₂-C₁₅ cycloalkenyl,        C₆-C₁₀ aryl, C₁-C₈ alkoxy, and fluorinated derivatives thereof;        and    -   (ii) a solvent for the metal coordination complex.

The metal in the metal coordination complex(es) employed in theabove-discussed method may comprise a metal selected from the groupconsisting of: Mg, Ca, Sr, Ba, Sc, Y, La, Ce, Ti, Zr, Hf, Pr, V, Nb, Ta,Nd, Cr, W, Pm, Mn, Re, Sm, Fe, Ru, Eu, Th, Lu, Pd, Pt, Ga, In, Au, Ag,Li, Na, K, Rb, Cs, Mo, Co, Rh, Ir, Gd, Ni, Tb, Cu, Dy, Ho, Al, Tl, Er,Sn, Pb, Tm, Bi, and Yb.

In such method the metal source reagent liquid solution may in someinstances comprise a multi-component solution including at least two ofthe aforementioned metal source complexes. The metal source reagentliquid solution may include solvent species selected such as: glymes,aliphatic hydrocarbons, aromatic hydrocarbons, ethers, esters, nitriles,and/or alcohols. The solvent may, for example, comprise at least onesolvent species selected from the group of solvents consisting of: glymesolvents having from 1 to 20 ethoxy —(C₂H₄₀)— repeat units; C₂-C₁₂alkanols, organic ethers selected from the group consisting of dialkylethers comprising C₁-C₆ alkyl moieties, C₄-C₈ cyclic ethers, andC₁₂-C₆₀-crown-O₄-O₂₀ ethers wherein the prefixed C_(i) range is thenumber i of carbon atoms in the ether compound and the suffixed O_(i)range is the number i of oxygen atoms in the ether compound; C₆-C₁₂aliphatic hydrocarbons; and C₆-C₁₈ aromatic hydrocarbons.

In yet a further aspect, the present invention relates to a method offorming a metal-containing film on a substrate, comprising providing ametal source reagent solution including a metal source reagent andsolvent medium, volatilizing the metal source reagent liquid solution toyield a metal source vapor, and contacting the metal source vapor withthe substrate, to deposit the metal-containing film thereon, wherein themetal source reagent(s) and the solvent medium are selected from thegroup, set out in Table I below, of metal source reagent(s) andassociated solvent media consisting of:

TABLE I Metal Source Reagent(s) Solvent Medium Al(thd)₃ 80-98%tetrahydrofuran and 2-20% tetraglyme Al(OR)₃ 80-98% tetrahydrofuran and2-20% tetraglyme Ba(thd)₂(tetraglyme) 85-99% butyl acetate and 1-15%tetraglyme Ca(thd)₂(tetraglyme) Cu(thd)₂ Ba(thd)₂(tetraglyme) 85-98%butyl acetate and 1-15% tetraglyme Sr(thd)₂(tetraglyme) Ti(OiPr)₂(thd)₂Ca(thd)₂(tetraglyme) 75-95% isopropanol with 5-25% tetraglymeSr(thd)₂(tetraglyme) Cr(thd)₃ 80-98% tetrahydrofuran with 2-20%tetraglyme Er(thd)₃ 85-99% butyl acetate and 1-15% tetraglyme Ir(acac)₃butyl acetate or Ir(thd)₃ La(thd)₃ tetrahydrofuran (MeO)₃P═O MgAl(OiPr)₈isopropanol Nb(OiPr)₄thd 45-88% tetrahydrofuran 10-35% isopropanol 2-20%tetraglyme Pb(thd)₂ 80-98% tetrahydrofuran and 2-20% tetraglyme La(thd)₃Ti(OiPr)₂(thd)₂ Pb(thd)₂ 80-98% tetrahydrofuran with 2-20% tetraglymeTi(OiPr)₂thd₂ Pb(thd)₂ 45-88% tetrahydrofuran Zr(thd)₄ 10-35%isopropanol 2-20% tetraglyme Pb(thd)₂ 45-88% tetrahydrofuran Zr(thd)₄10-35% isopropanol Ti(OiPr)₂(thd)₂ 2-20% tetraglyme Pb(thd)₂ 45-88%tetrahydrofuran Zr(thd)₄ 10-35% t-butanol Ti(OtBu)₂(thd)₂ 2-20%tetraglyme Ru(acac)₃ butyl acetate or Ru(thd)₃ Sn(alkyl)₂(β-diketonate)₂butyl acetate wherein alkyl = C₁-C₁₈ alkyl Sn(acetate)₂ butyl acetate or85-99% butyl acetate and 1-15% tetraglyme Sr(thd)₂(tetraglyme) 45-88%tetrahydrofuran BiPh₃ 10-35% isopropanol Ta(OiPr)₄(thd) 2-20% tetraglymeTa(OEt)₅ 1% ethanol solution [O═Ti(thd)₂]_(n) butyl acetate wherein n is1 or 2 Zr(thd)₄ 80-98% tetrahydrofuran and 2-20% tetraglyme Y(thd)₃[O═Zr(thd)₂]_(n) butyl acetate wherein n is 1 or 2 or butylacetate/tetraglyme Y(thd)₃ isopropanol Y(thd)₃ butyl acetate/tetraglymeBa(thd)₂ Cu(thd)₂ Cu(shfac)₂ 85-99% butyl acetate and 1-15% tetraglymeSr(shfac)₂ 85-99% butyl acetate and 1-15% tetraglyme Sr(sthd)₂ 85-99%butyl acetate and 1-15% tetraglyme Sr(sthd)₂ 85-99% butyl acetate and1-15% tetrathiocyclodecane Ca(sthd)₂ 85-99% butyl acetate and 1-15%tetraglyme Sr(sthd)₂ Ga(sthd)₃ Ce(sthd)₄ Ca(sthd)₂ 85-99% butyl acetateand 1-15% tetraglyme Ga(sthd)₃ Ce(sthd)₄ Ca(sthd)₂ 85-99% butyl acetateand 1-15% Sr(sthd)₂ tetrathiocyclodecane Ga(sthd)₃ Ce(sthd)₄ Cu(shfac)₂45-88% tetrahydrofuranacetate 10-35% isopropanol 2-20% tetraglymeCu(hfac)₂ 85-99% butyl acetate and 1-15% tetraglyme Sr(thd)₂ 85-99%butyl acetate and 1-15% tetraglyme Sr(thd)₂ 85-99% butyl acetate and1-15% tetrathiocyclodecane Cu(hfac)₂ 45-88% tetrahydrofuranacetate10-35% isopropanol 2-20% tetraglyme Ti(hfac)₃ 85-99% butyl acetate and1-15% tetraglyme Ti(hfac)₃ butyl acetate Mo(hfac)₃ butyl acetateMo(thd)₃ butyl acetatewherein when the solvent medium contains multiple solvent components,the percentages specified are percentages by weight, based on the weightof the total solvent medium, and with the total percentage of allsolvent components being 100%.

A further aspect of the invention relates to a method of forming a metalsulfide film on a substrate, comprising providing a metal source reagentsolution including a metal source reagent and solvent medium,volatilizing the metal source reagent liquid solution to yield a metalsource vapor, and contacting the metal source vapor with the substrate,optionally in the presence of a sulfur-containing gas, to deposit themetal-containing film thereon, wherein the metal source reagent(s) andthe solvent medium, are selected from the group, set out in Table IIbelow, of metal source reagent(s) and associated solvent mediaconsisting of:

TABLE II Cu(shfac)₂ 85-99% butyl acetate and 1-15% tetraglyme Sr(shfac)₂85-99% butyl acetate and 1-15% tetraglyme Sr(sthd)₂ 85-99% butyl acetateand 1-15% tetraglyme Sr(sthd)₂ 85-99% butyl acetate and 1-15%tetrathiocyclodecane Ca(sthd)₂ 85-99% butyl acetate and 1-15% tetraglymeSr(sthd)₂ Ga(sthd)₃ Ce(sthd)₄ Ca(sthd)₂ 85-99% butyl acetate and 1-15%tetraglyme Ga(sthd)₃ Ce(sthd)₄ Ca(sthd)₂ 85-99% butyl acetate and 1-15%Sr(sthd)₂ tetrathiocyclodecane Ga(sthd)₃ Ce(sthd)₄ Cu(shfac)₂ 45-88%tetrahydrofuran 10-35% isopropanol 2-20% tetraglyme Cu(hfac)₂ 85-99%butyl acetate and 1-15% tetraglyme Sr(thd)₂ 85-99% butyl acetate and1-15% tetraglyme Sr(thd)₂ 85-99% butyl acetate and 1-15%tetrathiocyclodecane Cu(hfac)₂ 45-88% tetrahydrofuran 10-35% isopropanol2-20% tetraglyme Ti(hfac)₃ 85-99% butyl acetate and 1-15% tetraglymeTi(hfac)₃ butyl acetate Mo(hfac)₃ butyl acetate Mo(thd)₃ butyl acetate.

The contacting of the metal source vapor with the substrate may thus becarried out in the presence of a sulfur-containing gas, e.g., asulfur-containing gas selected from the group of sulfur compoundsconsisting of hydrogen sulfide, t-butyl thiol, and cyclohexyl thiol.

In one particular aspect, the invention relates to a method of forming ametal sulfide film on a substrate, comprising providing a metal sourcereagent solution including a metal β-thioketonate source reagent andcompatible solvent medium for the metal β-thioketonate source reagent,volatilizing the metal source reagent liquid solution to yield a metalsource vapor, and contacting the metal source vapor with the substrate,to deposit the metal sulfide film thereon. Such contacting of the metalsource vapor with the substrate may advantageously be carried out in thepresence of hydrogen sulfide or other sulfur source gas or component.The metal moiety of such metal β-thioketonate source reagent may be ametal such as Cu, Sr, Ca, Ga, Ce, Ti, and Mo.

In another aspect, the invention relates to a method of forming ametal-containing film on a substrate, comprising providing a metalsource reagent solution including a metal source reagent and solventmedium, volatilizing the metal source reagent liquid solution to yield ametal source vapor, and contacting the metal source vapor with thesubstrate, to deposit the metal-containing film thereon, wherein thecomposition of the metal-containing film, metal source reagent, andsolvent medium, are selected from the group, set out in Table III below,consisting of:

TABLE III Metal Containing Film Metal Source Reagent Solvent MediumAl₂O₃ Al(thd)₃ tetrahydrofuran/tetraglyme Al₂O₃ Al(OR)₃tetrahydrofuran/tetraglyme BaCaCuO Ba(thd)₂(tetraglyme), butylacetate/tetraglyme Ca(thd)₂, Cu(thd)₂ Ba_(x)Sr_(1−x)TiO₃Ba(thd)₂(tetraglyme) butyl acetate/tetraglyme x = 0 to 1Sr(thd)₂(tetraglyme) Ti(OiPr)₂(thd)₂ BiSrCaCuO Sr(thd)₂(tetraglyme)isopropanol/tetraglyme; Ca(thd)₂(tetraglyme) Bi(C₆H₅)₃ Cu(thd) Cr₂O₃Cr(thd)₃ tetrahydrofuran/tetraglyme; Er doping Er(thd)₃ butylacetate/tetraglyme of SiO₂ Ir Ir(acac)_(3 or) butyl acetate Ir(thd)₃LaPO₄ La(thd)₃ tetrahydrofuran O═P(OMe)₃ MgAl₂O₄ MgAl₂(OiPr)₈isopropanol Nb₂O₅ Nb(OiPr)₄(thd) tetrahydrofuran/isopropanol/ tetraglymePbLa_(x)Ti_(1−x)O₃ Pb(thd)₂ tetrahydrofuran/tetraglyme La(thd)₃Ti(OiPr)₂(thd)₂ PbTiO₃ Pb(thd)₂ tetrahydrofuran/tetraglymeTi(OiPr)₂(thd)₂ PbZrO₃ Pb(thd)₂ tetrahydrofuran/isopropanol/ Zr(thd)₄tetraglyme PbZr_(x)Ti_(1−x)O₃ Pb(thd)₂ tetrahydrofuran/isopropanol/ x =0 to 1 Zr(thd)₄ tetraglyme Ti(OiPr)₂(thd)₂ PbZr_(x)Ti_(1−x)O₃ Pb(thd)₂tetrahydrofuran/tbutanol/ x = 0 to 1 Zr(thd)₄ tetraglyme Ti(OtBu)₂(thd)₂PbZr_(x)Ti_(1−x)O₃ Pb(thd)₂ tetrahydrofuran/isopropanol/ x = 0 to 1[O═Zr(thd)₂]_(n) tetraglyme, or [O═Ti(thd)₂]_(n) butylacetate/tetraglyme n = 1 or 2 RuO₂ Ru(acac)₃ or butyl acetate Ru(thd)₃SnO₂ Sn(alkyl)₂ (β-diketonate)₂ butyl acetate alkyl = C₁-C₁₈ SnO₂Sn(acetate)₂ butyl acetate SrBi₂Ta₂O₉ Sr(thd)₂ tetraglymetetrahydrofuran/isopropanol/ BiPh₃ tetraglyme Ta(OiPr)₄thd Ta₂O₅Ta(OEt)₅ ethanol Ta₂O₅ Ta(OR)₄(thd) tetrahydrofuran/isopropanol/ R =ethyl, isopropyl tetraglyme TiO₂ [O═Ti(thd)₂]_(n) butylacetate/tetraglyme n = 1 or 2 V₂O₅ O═V(thd)₃ butyl acetate/tetraglyme.Y₂O₃—ZrO₂ Zr(thd)₄ tetrahydrofuran/tetraglyme; Y(thd)₃ Y₂O₃ Y(thd)₃isopropanol YBaCuO Y(thd)₃ butyl acetate/tetraglyme Ba(thd)₂(tetraglyme)or tetraglyme Cu(thd)₂ ZrO₂ [O═Zr(thd)₂]_(n) butyl acetate/tetraglyme n= 1 or 2 CuS Cu(shfac)₂ butyl acetate/tetraglyme SrS Sr(shfac)₂ butylacetate/tetraglyme SrS Sr(sthd)₂ butyl acetate/tetraglyme SrS Sr(sthd)₂butyl acetate/tetrathiocyclodecane (Ca,Sr)Ga₂S₄, Ca(sthd)₂ butylacetate/tetraglyme cerium-doped Sr(sthd)₂ Ga(sthd)₃ Ce(sthd)₄(Ca,Sr)Ga₂S₄, Ca(sthd)₂ butyl acetate/tetrathiocyclodecane cerium-dopedSr(sthd)₂ Ga(sthd)₃ Ce(sthd)₄ CuS Cu(shfac)₂ tetrahydrofuranacetateisopropanol tetraglyme CuS Cu(hfac)₂ butyl acetate/tetraglyme SrSSr(thd)₂ butyl acetate/tetraglyme SrS Sr(thd)₂ butylacetate/tetrathiocyclodecane CuS Cu(hfac)₂ tetrahydrofuranacetateisopropanol tetraglyme TiS₂ Ti(hfac)₃ butyl acetate/tetraglyme TiS₂Ti(hfac)₃ butyl acetate MoS₂ Mo(hfac)₃ butyl acetate MoS₂ Mo(thd)₃ butylacetate.

In the method discussed above with reference to Table III, thecontacting of the metal source vapor with the substrate may be carriedout in the presence of a sulfur-containing gas, e.g., hydrogen sulfide,t-butylthiol, and cyclohexylthiol. Alternatively, the solvent mediumcontains a sulfur compound therein, such as hydrogen sulfide,t-butylthiol and cyclohexyl thiol.

In the above-discussed method, the metal sulfide film may advantageouslybe reacted with a metal-coreactant to form a binary metal sulfide filmon the substrate.

In a preferred aspect of the present invention, the metal-organic sourcereagent-containing liquid compositions employed to carry out thechemical vapor deposition (CVD) process are stabilized in character,meaning that the metal-organic source reagent therein is resistant todegradation via ligand exchange reactions, e.g., non-degenerative ligandexchanges which adversely affect the chemical identity and suitabilityof the reagent compositions for CVD applications.

Such metal source reagent liquid solutions advantageously comprise:

-   -   (i) at least one metal coordination complex, each of such metal        coordination complexes including a metal coordinatively binding        at least one ligand in a stable complex, wherein such at least        one ligand is selected from the group consisting of        β-diketonates and β-ketoesters, and their sulfur and nitrogen        analogs (i.e., corresponding ligands containing S or N atoms in        place of the O atom(s) in the β-diketonates and β-ketoesters);        and    -   (ii) a solvent for such metal coordination complex(es).

A generalized formula for each of such metal coordination complexes is

M^(i)A_(a)(OR)_(x)B_(y)Q_(z)

wherein:

-   -   M is a metal selected from the group consisting of Mg, Ca, Sr,        Ba, Sc, Y, La, Lu, Ce, Ti, Zr, Hf, Pr, V, Nb, Ta, Nd, Cr, W, Pm,        Mn, Re, Sm, Fe, Ru, Eu, Co, Rh, Ir, Gd, Ni, Tb, Th, Cu, Dy, Ho,        Al, Tl, Er, Sn, Pb, Pd, Pt, Ga, In, Au, Ag, Li, Na, K, Rb, Cs,        Mo, Tm, Bi, and Yb;    -   A is selected from the group consisting of β-diketonates and        β-ketoesters, and their sulfur and nitrogen analogs;    -   R is selected from the group consisting of C₁-C₈ alkyl, C₂-C₈        cycloalkyl, C₂-C₁₀ alkenyl, C₂-C₁₅ cycloalkenyl, C₆-C₁₀ aryl,        and (fully or partially) fluorinated derivatives thereof (i.e.,        wherein hydrogen substituent(s) of the C₁-C₈ alkyl, C₂-C₈        cycloalkyl, C₂-C₁₀ alkenyl, C₂-C₁₅ cycloalkenyl, or C₆-C₁₀ aryl        ligand, is/are replaced by fluorine substituent(s));    -   B is selected from the group consisting of polyethers,        polyamines, polythiols, bipyridines, glymes, alcohols, crown        ethers, crown thioethers, cyclic polyamines (cyclenes),        thioglymes, arylthiols, and aliphatic thiols (mercaptans).    -   Q is hydrocarbyl or halohydrocarbyl, e.g., a ligand selected        from the group consisting of C₁-C₈ alkyl, C₂-C₈ cycloalkyl,        C₂-C₁₀ alkenyl, C₂-C₁₅ cycloalkenyl, C₆-C₁₀ aryl, and        fluorinated derivatives thereof;    -   a, x, y, and z are stoichiometric coefficients for the ligands        A, OR, B, and Q, respectively, wherein a is ≧1; each of x, y,        and z is independently ≧0; and A_(a)(OR)_(x)B_(y)Q_(z) is in        stoichiometric relationship to metal M.

Thus, each of the metal complexes in such solutions comprises at leastone ligand A coordinated to the central atom M of the complex, and M mayoptionally have additionally coordinated thereto one or more of theligands OR, B, and Q, in which the resulting complex is appropriatelystoichiometrically constituted to define a stable complex.

One class of source reagent complexes usefully employed in reagentsolutions in the process of the invention comprise those of the formula:

M(R²—C(O)—CH—C(G)-R³)_(a)(OR)_(x)

wherein:

-   -   a, x, M and R are as defined hereinabove;    -   R² and R³ are independently selected from C₁-C₈ alkyl, C₂-C₈        cycloalkyl, C₂-C₁₀ alkenyl, C₂-C₁₅ cycloalkenyl, C₆-C₁₀ aryl,        and fluorinated derivatives thereof; and    -   G is oxygen, sulfur, or nitrogen moiety of the formula ═NR_(b)        in which R_(b) is selected from the group consisting of H, C₁-C₈        alkyl, C₂-C₈ cycloalkyl, C₂-C₁₀ alkenyl, C₂-C₁₅ cycloalkenyl,        C₆-C₁₀ aryl, and fluorinated derivatives thereof.

The solvent utilized in the source reagent solutions in the process ofthe invention may comprise any suitable solvent species, or combinationof solvent species, with which the metal complexes are compatible, suchas aliphatic hydrocarbons, aromatic hydrocarbons, ethers, esters,nitriles, and alcohols. The solvent component of the solution preferablycomprises a solvent selected from the group consisting of: glymesolvents having from 1 to 20 ethoxy —(C₂H₄O)— repeat units; C₂-C₁₂alkanols, organic ethers selected from the group consisting of dialkylethers comprising C₁-C₆ alkyl moieties, C₄-C₈ cyclic ethers;C₁₂-C₆₀-crown-O₄-O₂₀ ethers wherein the prefixed C_(i) range is thenumber i of carbon atoms in the ether compound and the suffixed O_(i)range is the number i of oxygen atoms in the ether compound; C₆-C₁₂aliphatic hydrocarbons; C₆-C₁₈ aromatic hydrocarbons; organic esters;organic amines; and polyamines.

As used herein, the term “stable complex” means that the metal sourcecomplex in a pure state (unexposed to other materials, such as water,oxygen, etc.) is not susceptible to spontaneous degradation ordecomposition at 25 degrees Centigrade and 1 atmosphere pressure. Theterm “complex” is intended to be broadly construed to encompasscompounds as well as coordination complexes wherein at least one metalatom is coordinated (covalently, ionically and/or associatively) to atleast one organic ligand group.

In yet another aspect, the process of the present invention may utilizea source reagent liquid solution comprising:

-   -   (i) at least one, and preferably at least two, metal        coordination complexes, each of the formula:

M^(i)A_(a)(OR)_(x)B_(y)Q_(z)

wherein:

-   -   M is a metal selected from the group consisting of Mg, Ca, Sr,        Ba, Sc, Y, La, Ce, Ti, Zr, Hf, Pr, V, Nb, Ta, Nd, Cr, W, Pm, Mn,        Re, Sm, Fe, Ru, Eu, Co, Rh, Ir, Gd, Ni, Tb, Cu, Dy, Ho, Al, Tl,        Er, Sn, Pb, Tm, Bi, Lu, Th, Pd, Pt, Ga, In, Au, Ag, Li, Na, K,        Rb, Cs, Mo, and Yb;    -   A is selected from the group consisting of β-diketonates and        β-ketoesters, and their sulfur and nitrogen analogs;    -   R is selected from the group consisting of C₁-C₈ alkyl, C₂-C₈        cycloalkyl, C₂-C₁₀ alkenyl, C₂-C₁₅ cycloalkenyl, C₆-C₁₀ aryl,        and (fully or partially) fluorinated derivatives thereof (i.e.,        wherein hydrogen substituent(s) of the C₁-C₈ alkyl, C₂-C₈        cycloalkyl, C₂-C₁₀ alkenyl, C₂-C₁₅ cycloalkenyl, or C₆-C₁₀ aryl        ligand, is/are replaced by fluorine substituent(s));    -   B is selected from the group consisting of polyethers,        polyamines, polythiols, bipyridines, glymes, alcohols, crown        ethers, crown thioethers, cyclic polyamines (cyclenes),        thioglymes, arylthiols, and aliphatic thiols (mercaptans).    -   Q is hydrocarbyl or halohydrocarbyl, e.g., a ligand selected        from the group consisting of C₁-C₈ alkyl, C₂-C₈ cycloalkyl,        C₂-C₁₀ alkenyl, C₂-C₁₅ cycloalkenyl, C₆-C₁₀ aryl, and        fluorinated derivatives thereof;    -   a, x, y, and z are stoichiometric coefficients for the ligands        A, OR, B, and Q, respectively, wherein a is ≧1; each of x, y,        and z is independently ≧0, and A_(a)(OR)_(x)B_(y)Q_(z) is in        stoichiometric relationship to metal M; and    -   (ii) a solvent for the metal coordination complex(es).

The process of the present invention in another aspect may utilizesolutions containing compounds comprised of β-diketonate and/or alkoxideligands having a metal M, e.g., selected from the group consisting ofMg, Ca, Sr, Ba, Sc, Y, La, Ce, Ti, Zr, Hf, Pr, V, Nb, Ta, Nd, Cr, W, Pm,Mn, Re, Sm, Fe, Ru, Eu, Co, Rh, Ir, Gd, Ni, Tb, Cu, Dy, Ho, Al, Tl, Er,Sn, Pb, Tm, Bi, Lu, Th, Pd, Pt, Ga, In, Au, Ag, Li, Na, K, Rb, Cs, Mo,and Yb, complexed to at least one alkoxide ligand and at least oneβ-diketonate ligand.

Such compounds may have the general formula:

M(OR¹)_(x)(R²—C(G)-CH—C(G)-R³)_(y)

wherein:

-   -   G is oxygen, sulfur, or imide of the formula: ═NR_(b), wherein        Rb is H, C₁-C₈ alkyl, or C₁-C₈ perfluoroalkyl (e.g.,        trifluoroethyl);    -   x+y=p where p is the valence of metal M;    -   x+2y=q where q is the coordination number of the metal M;    -   R¹ is C₁-C₆ hydrocarbyl or fluoroalkyl;    -   R² and R³ are independently selected from C₁-C₁₄ hydrocarbyl,        C₁-C₆ alkoxy, and C₂-C₆ fluoroalkyl groups, wherein hydrocarbyl        groups may be selected from C₁-C₈ alkyl, C₆-C₁₀ cycloalkyl,        C₂-C₁₂ alkenyl and C₆-C₁₄ aryl groups, and C₁-C₆ fluoroalkyl        groups may be selected from perfluoroalkyls of 2 through 6        carbons.

Preferred compounds of such type comprise M(OtBu)₂(thd)₂ whereinM=titanium or zirconium, OtBu=t-butoxy and thd is defined below.

As used herein, the following terms for ligand groups have the followingmeanings: acac=acetylacetonate, more specifically 2,4-pentane dionate;hfacac (or hfac)=hexafluoroacetylacetonate, more specifically1,1,1,5,5,5-hexafluoro-2,4-pentanedionate; tfacac (ortfac)=trifluoroacetylacetonate, more specifically1,1,1-trifluoro-2,4-pentanedionate; thd=tetramethylheptanedionate, ashereinabove identified, and more specifically2,2,6,6-tetramethyl-3,5-heptanedionate; fod=fluorodimethyloctanedionate,more specifically1,1,1,2,2,3,3-heptafluoro-7,7-dimethyl-4,6-octanedionate;hfod=heptafluoro-dimethyloctanedionate; and tg=tetraglyme. Thecorresponding β-thioketonate ligands are identified consistentlytherewith, by prefixation of “s” to the corresponding β-diketonateligand, e.g., shfac, sthd, etc.

The invention relates in one aspect to a metalorganic complexcomposition comprising a metalorganic complex selected from the groupconsisting of:

metalorganic complexes comprising one or more metal central atomscoordinated to one or more monodentate or multidentate organic ligands,and complexed with one or more complexing monodentate or multidentateligands containing one or more atoms independently selected from thegroup consisting of atoms of the elements C, N, H, S, O and F;wherein when the number of metal atoms is one and concurrently thenumber of complexing monodentate or multidentate ligands is one, thenthe complexing monodentate or multidentate ligand of the metalorganiccomplex is selected from the group consisting of beta-ketoiminates,beta-diiminates, C₂-C₁₀ alkenyl, C₂-C₁₅ cycloalkenyl and C₆-C₁₀ aryl.

Additional aspects of the invention relate to methods of forming on asubstrate a metal film, comprising depositing said metal film on saidsubstrate via chemical vapor deposition from a metalorganic complexesand compositions of the invention.

When identified herein by reference to generalized formulas, the copperoxide compound formulas YBaCuO, BaCaCuO, and BiSrCaCuO are intended tobe construed to encompass the corresponding stoichiometricallyappropriate specific stoichiometries (i.e., specific stoichiometriccoefficients w, x, y, and z) of the metal moieties, in relation to theother metal components and the oxygen constituent of such compounds,that yield stable forms of the metal oxide compounds at 25° C. and 1atmosphere pressure. More generally, various reagents and depositedproducts may be referred to sometimes hereinafter by alphabetic acronymsbased on their constituent elements or moieties, e.g., PZT for leadzirconium titanate, BST for barium strontium titanate, etc., and in suchcase, such acronymic designations are intended to be broadly construedto encompass all suitable stoichiometric forms of the composition underconsideration.

It is to be appreciated that the compositions disclosed herein, inrespect of constituent components and/or moieties of such compositions,may comprise, consist, and/or consist essentially of, such constituentcomponents and/or moieties.

Other aspects and features of the invention will be more fully apparentfrom the ensuing disclosure and appended claims.

DETAILED DESCRIPTION OF THE INVENTION, AND PREFERRED EMBODIMENTS THEREOF

The disclosures of the following prior applications and appertainingpatents hereby are incorporated herein in their entirety: U.S. patentapplication Ser. No. 09/649,549 filed Aug. 28, 2000; U.S. patentapplication Ser. No. 08/484,654 filed Jun. 7, 1995 (U.S. Pat. No.6,110,529); U.S. patent application Ser. No. 08/414,504 filed Mar. 31,1995 (U.S. Pat. No. 5,820,664); U.S. patent application Ser. No.08/280,143 filed Jul. 25, 1994 (U.S. Pat. No. 5,536,323); U.S. patentapplication Ser. No. 07/927,134, filed Aug. 7, 1992; U.S. patentapplication Ser. No. 07/807,807, filed Dec. 31, 1991 (U.S. Pat. No.5,204,314); U.S. patent application Ser. No. 07/549,389, filed Jul. 6,1990; U.S. application Ser. No. 08/181,800 filed Jan. 15, 1994 (U.S.Pat. No. 5,453,494); U.S. patent application Ser. No. 07/918,141 filedJul. 22, 1992 (U.S. Pat. No. 5,280,012); U.S. patent application Ser.No. 07/615,303 filed Nov. 19, 1990; U.S. patent application Ser. No.07/581,631 filed Sep. 12, 1990 (U.S. Pat. No. 5,225,561).

The present invention generally relates to chemical vapor deposition(CVD) processes utilizing metal-organic source reagent compositions, andliquid compositions containing such metal-organic source reagentcompositions, which are suitably stable, e.g., resistant to deleteriousligand exchange. More specifically, the metal source reagentcompositions used in processes of the present invention comprisecompounds or coordination complexes in which the metal atoms arecoordinated to ligand species which are organic in character, asdiscussed in the preceding Summary section herein.

The ligand groups of the metal source complexes in the broad practice ofthe present invention may be variously substituted to realize a widevariety of materials to optimize volatility, stability and film purity.Preferably, when the metal source reagent comprises a multi-componentsolution including two or more metal source complexes, the ligands ofthe various metal source complexes should be either (a) identical toresult in degenerative ligand exchange (wherein any ligand exchangeinvolves replacement of the ligand group by the same type ligand fromanother constituent of the multicomponent solution), or (b) resistant toany detrimental non-degenerative ligand exchange in relation to oneanother which would substantially impair or preclude the efficacy of themetal source complex for its intended purpose.

The ligand groups that are potentially useful in metal source reagentsof the present invention include the ligands which are more fullydisclosed in U.S. Pat. No. 5,225,561, the disclosure of which hereby isincorporated herein in its entirety.

The metal source reagents are selected for solution applications on thebasis of the following criteria: (i) the metal centers in thecoordinated complexes should be as coordinatively saturated as possible,and in such respect multidentate ligands are preferred which occupymultiple coordination sites in the source reagent complex; (ii) theligands preferably comprise sterically bulky groups such as isopropyl,t-butyl, and neopentyl, which prevent close approach of the metalcenters and thus hinder deleterious ligand exchange reactions whichmight otherwise occur; and (iii) each individual metal source reagent inthe solution has a suitable vapor pressure characteristic, e.g., a vaporpressure of at least 0.001 Torr at the temperature and pressureconditions involved in their volatilization.

The solvent medium employed in source reagent solutions in accordancewith the present invention may be any suitable organic solvent which iscompatible with the metal complexes in the solution, has moderatevolatility, and in which high concentrations of the metal complexes canbe dissolved. Such solvent medium may suitably comprise one or moresolvent species such as: glymes, aliphatic hydrocarbons, aromatichydrocarbons, organic ethers (including dialkyl, cyclic and crownethers), dialkyl esters, alkyl nitriles (═NR_(b), wherein Rb is H, C₁-C₈alkyl, or C₁-C₈ perfluoroalkyl, e.g., trifluoroethyl), and alkanols.Among these classes of solvents, preferred solvent species include glymesolvents having from 1 to 20 ethoxy —(C₂H₄O)— repeat units; C₂-C₁₂alkanols, organic ethers selected from the group consisting of dialkylethers comprising C₁-C₆ alkyl moieties, C₄-C₈ cyclic ethers, and C₁₂-C₆₀crown O₄-O₂₀ ethers wherein the prefixed C_(i) range is the number i ofcarbon atoms in the ether compound and the suffixed O_(i) range is thenumber i of oxygen atoms in the ether compound; C₆-C₁₂ aliphatichydrocarbons; and C₆-C₁₈ aromatic hydrocarbons. Particularly preferredcrown ethers include 12-crown-4,15-crown-5, and 18-crown-6 species.

Preferred metal source reagent species include compounds having asconstitutent moieties thereof β-diketonate and alkoxide ligands, and ametal selected from the group consisting of Mg, Ca, Sr, Ba, Sc, Y, La,Ce, Ti, Zr, Hf, Pr, V, Nb, Ta, Nd, Cr, W, Pm, Mn, Re, Sm, Fe, Ru, Eu,Co, Rh, Ir, Gd, Ni, Tb, Cu, Dy, Ho, Al, Tl, Er, Sn, Pb, Tm, Bi, Lu, Th,Pd, Pt, Ga, In, Au, Ag, Li, Na, K, Rb, Cs, Mo, and Yb, wherein the metalis coordinated to at least one alkoxide ligand and at least oneβ-diketonate ligand.

Illustrative β-diketonate ligands employed in metal source complexes ofthe present invention include acac, thd, fod, hfod, tfacac, and hfacac,and their corresponding nitrogen and thio analogs (i.e., wherein oxygenin the β-diketonate is replaced by nitrogen or sulfur, respectively).

By way of example, the metal source reagent liquid solutions of thepresent invention may suitably comprise metal source reagent and solventmedium species identified in Table IV set out below.

TABLE IV Metal Source Reagent(s) Solvent Medium Al(thd)₃ tetrahydrofuranwith 10% tetraglyme; Al(OR)₃ tetrahydrofuran with 10% tetraglyme;Ba(thd)₂(tetraglyme), 25:1 butyl acetate/tetraglyme; Ca(thd)₂, Cu(thd)₂Ba(thd)₂(tetraglyme), 25:1 butyl acetate/tetraglyme;Sr(thd)₂(tetraglyme), Ti(OiPr)₂(thd)₂ Sr(thd)₂ 10:1isopropanol/tetraglyme; Ca(thd)₂ Cr(thd)₃ 9:1tetrahydrofuran/tetraglyme; Er(thd)₃ butyl acetate Ir(acac)_(3 or) butylacetate Ir(thd)₃ La(thd)₃ tetrahydrofuran (MeO)₃P═O MgAl₂(OiPr)₈isopropanol Nb(OiPr)₄(thd) 8:2:1 tetrahydrofuran/isopropanol/ tetraglymePb(thd)₂ 9:1 tetrahydrofuran/tetraglyme; La(thd)₃ Ti(OiPr)₂(thd)₂Pb(thd)₂ 9:1 tetrahydrofuran/tetraglyme; Ti(OiPr)₂(thd)₂ Pb(thd)₂ 8:2:1tetrahydrofuran/isopropanol/ Zr(thd)₄ tetraglyme Pb(thd)₂ 8:2:1tetrahydrofuran/isopropanol/ Zr(thd)₄ tetraglyme Ti(OiPr)₂(thd)₂Pb(thd)₂ 8:2:1 tetrahydrofuran/t-butanol/ Zr(thd)₄ tetraglymeTi(OtBu)₂(thd)₂ Ru(acac)_(3 or) butyl acetate Ru(thd)₃ Sn(alkyl)₂ (β-butyl acetate diketonate)₂ alkyl = C₁-C₈ alkyl Sn(acetates)₂ butylacetate or 25:1butyl acetate/tetraglyme Sr(thd)₂ (tetraglyme) 8:2:1tetrahydrofuran/isopropanol/ BiPh₃ tetraglyme Ta(OiPr)₄thd Ta(OEt)₅ neatwith 1% ethanol or ethanol [O═Ti(thd)₂]_(n) butyl acetate or wherein nis 1 or 2 25:1 butyl acetate/tetraglyme Y(thd)₃ isopropanol Y(thd)₃ 25:1butyl acetate/tetraglyme Ba(thd)₂ Cu(thd)₂ Zr(thd)₄ 9:1tetrahydrofuran/tetraglyme; Y(thd)₃ [O═Zr(thd)₂]_(n) butyl acetatewherein n is 1 or 2 or 25:1 butyl acetate/tetraglyme Y(thd)₃ isopropanolY(thd)₃ 25:1 butyl acetate/tetraglyme Ba(thd)₂ Cu(thd)₂ Zr(thd)₄ 9:1tetrahydrofuran/tetraglyme; Y(thd)₃ [O═Zr(thd)₂]_(n) butyl acetatewherein n is 1 or 2 or 25:1 butyl acetate/tetraglyme Cu(shfac)₂ 25:1butyl acetate/tetraglyme Sr(shfac)₂ 25:1 butyl acetate/tetraglymeSr(sthd)₂ 25:1 butyl acetate/tetraglyme Sr(sthd)₂ butylacetate/tetrathiocyclodecane Ca(sthd)₂ 25:1 butyl acetate/tetraglymeSr(sthd)₂ Ga(sthd)₃ Ce(sthd)₄ Ca(sthd)₂ 25:1 butyl acetate/tetraglymeGa(sthd)₃ Ce(sthd)₄ Cu(shfac)₂ 8:25:1isopropanol/tetrahydrofuran/tetraglyme Ca(sthd)₂ 25:1 butylacetate/tetrathiocyclodecane Sr(sthd)₂ Ga(sthd)₃ Ce(sthd)₄ Cu(hfac)₂25:1 butyl acetate/tetraglyme Sr(thd)₂ 25:1 butylacetate/tetrathiocyclodecane Cu(hfac)₂ 8:25:1isopropanol/tetrahydrofuran/tetraglyme Ti(hfac)₃ 25:1 butylacetate/tetraglyme Ti(hfac)₃ butyl acetate Mo(hfac)₃ butyl acetateMo(thd)₃ butyl acetate

The metal source reagent solutions employed in the process of thepresent invention may be readily employed in CVD applications forforming a metal-containing film on a substrate, by the steps ofvolatilizing the metal source reagent liquid solution to yield a metalsource vapor, and contacting the metal source vapor with the substrate,to deposit the metal-containing film thereon. Illustrative metal sourcereagent solutions and corresponding metal-containing film compositionsare identified in Table III hereinabove in the “Summary of theInvention” section hereof.

One class of metal complex compositions of the invention includes ametalorganic complex selected from the group consisting of:

metalorganic complexes comprising one or more metal central atomscoordinated to one or more monodentate or multidentate organic ligands,and complexed with one or more complexing monodentate or multidentateligands containing one or more atoms independently selected from thegroup consisting of atoms of the elements C, N, H, S, O and F;wherein when the number of metal atoms is one and concurrently thenumber of complexing monodentate or multidentate ligands is one, thenthe complexing monodentate or multidentate ligand of the metalorganiccomplex is selected from the group consisting of beta-ketoiminates,beta-diiminates, C₂-C₁₀ alkenyl, C₂-C₁₅ cycloalkenyl and C₆-C₁₀ aryl.

Such metalorganic complex composition can include any suitable metal(s),such as for example Cu, Ba, Sr, La, Nd, Ce, Pr, Sm, Eu, Th, Gd, Tb, Dy,Ho, Er, Tm, Yb, Lu, Pm, Mn, Re, Lu, Bi, Tl, Y, Pb, Ni, Pd, Pt, Al, Ga,In, Ag, Au, Co, Rh, Ir, Fe, Ru, Sn, Sc, Li, Na, K, Rb, Cs, Ca, Mg, Ti,Zr, Hf, V, Nb, Ta, Cr, Mo, and/or W.

The metalorganic complex composition in one aspect comprises a solventmedium. The solvent medium can be a solvent mixture, or a single solventspecies. Illustrative solvent species include, without limitation,solvents such as glymes, aliphatic hydrocarbons, aromatic hydrocarbons,ethers, esters, nitriles, and alcohols, and mixtures of two or moresolvents of the foregoing listing. Preferred solvents in respect of somecompositions of the invention include tetrahydrofuran, tetraglyme, butylacetate, isopropanol, ethanol, tetrathiocyclodecane, andtetrahydrofuranecetate.

The metalorganic complex composition of the invention, wherein one ormore of the monodentate or multidentate organic ligands comprises abeta-diketonate, can include beta-diketonates such as acac, hfac, tfac,thd, fod, and hfod. The metalorganic complex in the composition cancomprise two different beta-diketonate ligands of any suitable type,such as the above-mentioned species of acac, hfac, tfac, fod, and hfod.

Alternatively, such one or more monodentate or multidentate organicligands can include a beta-ketoiminate or a beta-diiminate.

One class of source reagent compositions usefully employed in theprocess of the present invention includes source reagent liquidsolutions comprising:

-   -   (i) at least one, and preferably at least two, metal        coordination complexes, each of the formula:

M^(i)A_(a)(OR)_(x)B_(y)Q_(z)

wherein:

-   -   M is a metal selected from the group consisting of Mg, Ca, Sr,        Ba, Sc, Y, La, Ce, Ti, Zr, Hf, Pr, V, Nb, Ta, Nd, Cr, W, Pm, Mn,        Re, Sm, Fe, Ru, Eu, Co, Rh, Ir, Gd, Ni, Tb, Cu, Dy, Ho, Al, Tl,        Er, Sn, Pb, Tm, Bi, Lu, Th, Pd, Pt, Ga, In, Au, Ag, Li, Na, K,        Rb, Cs, Mo, and Yb;    -   A is selected from the group consisting of β-diketonates and        β-ketoesters, and their sulfur and nitrogen analogs;    -   R is selected from the group consisting of C₁-C₈ alkyl, C₂-C₈        cycloalkyl, C₂-C₁₀ alkenyl, C₂-C₁₅ cycloalkenyl, C₆-C₁₀ aryl,        and (fully or partially) fluorinated derivatives thereof (i.e.,        wherein hydrogen substituent(s) of the C₁-C₈ alkyl, C₂-C₈        cycloalkyl, C₂-C₁₀ alkenyl, C₂-C₁₅ cycloalkenyl, or C₆-C₁₀ aryl        ligand, is/are replaced by fluorine substituent(s));    -   B is selected from the group consisting of polyethers,        polyamines, polythiols, bipyridines, glymes, alcohols, crown        ethers, crown thioethers, cyclic polyamines (cyclenes),        thioglymes, arylthiols, and aliphatic thiols (mercaptans).    -   Q is hydrocarbyl or halohydrocarbyl, e.g., a ligand selected        from the group consisting of C₁-C₈ alkyl, C₂-C₈ cycloalkyl,        C₂-C₁₀ alkenyl, C₂-C₁₅ cycloalkenyl, C₆-C₁₀ aryl, and        fluorinated derivatives thereof;    -   a, x, y, and z are stoichiometric coefficients for the ligands        A, OR, B, and Q, respectively, wherein a is ≧1; each of x, y,        and z is independently ≧0, and A_(a)(OR)_(x)B_(y)Q_(z) is in        stoichiometric relationship to metal M; and    -   (ii) a solvent for the metal coordination complex(es).

Another class of source reagent solutions usefully employed in theprocess of the present invention contain β-diketonate alkoxide compoundshaving a metal M selected from the group consisting of Mg, Ca, Sr, Ba,Sc, Y, La, Ce, Ti, Zr, Hf, Pr, V, Nb, Ta, Nd, Cr, W, Pm, Mn, Re, Sm, Fe,Ru, Eu, Co, Rh, Ir, Gd, Ni, Tb, Cu, Dy, Ho, Al, Tl, Er, Sn, Pb, Tm, Bi,Lu, Th, Pd, Pt, Ga, In, Au, Ag, Li, Na, K, Rb, Cs, Mo, and Yb, complexedto at least one alkoxide ligand and at least one β-diketonate ligand, inwhich the compounds have the following formula:

M(OR¹)_(x)(R²—C(G)-CH—C(G)-R³)_(y)

wherein:G is oxygen, sulfur, or imide of the formula: ═NR_(b), wherein Rb is H,C₁-C₈ alkyl, or C₁-C₈ perfluoroalkyl (e.g., trifluoroethyl);x+y=p where p is the valence of metal M;x+2y=q where q is the coordination number of the metal M;R¹ is C₁-C₆ hydrocarbyl or fluoroalkyl;

R² and R³ are independently selected from C₁-C₁₄ hydrocarbyl, C₁-C₆alkoxy, and C₂-C₆ fluoroalkyl groups, wherein hydrocarbyl groups may beselected from C₁-C₈ alkyl, C₆-C₁₀ cycloalkyl, C₂-C₁₂ alkenyl and C₆-C₁₄aryl groups, and C₁-C₆ fluoroalkyl groups may be selected fromperfluoroalkyls of 2 through 6 carbons.

R¹ is preferably C₁-C₆ alkyl, preferably methyl, ethyl, propyl,n-propyl, i-propyl, n-butyl, s-butyl, or t-butyl, and most preferablyethyl, i-propyl, or t-butyl. R² and R³ are preferably selected from theC₂-C₆ alkyl or cycloalkyl groups t-butyl, s-butyl, i-propyl, cyclohexyl,or neopentyl, and most preferably t-butyl, s-butyl, or isopropyl.

Preferred alkoxy metal beta-diketonate compositions of the inventioncomprise M(OtBu)₂(thd)₂ wherein M=titanium or zirconium, OtBu=t-butoxyand thd=tetramethylheptanedionate.

The various source reagent metal complexes employed in the process ofthe invention may be readily made by conventional synthetic techniques,including those more fully described in U.S. Pat. No. 5,225,561, thedisclosure of which hereby is incorporated herein by reference. Theresulting reagent metal complexes may readily be formulated intosolution form, by conventional dissolution and solubilizationtechniques, for subsequent use as CVD source reagents having good shelflife characteristics and which are substantially stable in storage atambient conditions (e.g., room temperature). The reagent solutions maysubsequently be readily vaporized by suitable reagent delivery systemssuch as those described in U.S. Pat. No. 5,204,314, the disclosure ofwhich also is hereby incorporated herein by reference.

The features and advantages of the invention are more fully shown by thefollowing non-limiting examples, wherein all parts and percentages areby weight unless otherwise expressly stated.

Example 1 Synthesis of Ta(OEt)₄(η²-thd)

One equivalent (33.9 g) of 2,2,6,6-tetramethyl-3,5-heptanedione (Hthd)was added directly to 74.6 g Ta(OEt)₅ in a 500 mL Schlenk flask; bothstarting materials were obtained commercially (Lancaster Chemicals,Inc.). The vessel was heated to 65° C. under a slow nitrogen purge to abubbler. After 2 hours, the ethanol generated was removed in vacuo toyield 99.8 g of the colorless liquid Ta(OEt)₄(η²-thd) in quantitativeyield, which solidified upon cooling. The compound melted at 26° C. andboiled at approximately 80° C. at 140 mtorr. The ¹H and ¹³C NMR spectrain benzene-d₆ were consistent with an octahedral structure composed oftwo ethoxide ligands in axial positions and a second set of cis-ethoxideligands in the equatorial plane across from the bidentate β-diketonate:d 5.81 (s, 1H, CH), 4.72 (q, 4H, CH₂), 4.20 (q, 4H, CH₂), 1.34 (tr, 6H,CH₃), 1.14 (tr, 6 H, CH₃), 1.13 (s, 18H, t-Bu); ¹³C{¹H} NMR (C₆D₆) d199.9 (CO), 92.9 (CH_(diket)), 68.8 (CH₂CH₃), 65.4 (CH₂CH₃), 40.9(CMe₃), 28.3 (CMe ₃), 19.6 (CH₂ CH₃), 19.0 (CH₂ CH₃).

Example 2 Synthesis of Ta(OiPr)₄(η²-thd)

A nine-fold excess of isopropanol (170 mL) was added to 33.6 gTa(OEt)₄(η²-thd). The solution was heated at 60° C. for 45 min,following which the volatiles were removed in vacuo. The ligand exchangeprocedure was repeated a second time to yield 36.8 g of white,crystalline Ta(O-i-Pr)₄(η²-thd) in quantitative yield. The product waspurified by sublimation at 100° C. at 150 mtorr. The compound melted at149° C. The ¹H and ¹³C NMR spectra in benzene-d₆ were consistent with anoctahedral structure composed of two isopropoxide ligands in axialpositions and a second set of cis-isopropoxide ligands in the equatorialplane across from the bidentate b-diketonate: d 5.81 (s, 1H, CH), 5.10(sept, 2H, CH), 4.51 (sept, 2H, CH), 1.38 (d, 12H, Me), 1.20 (d, 12H,Me), 1.17 (s, 18 H, t-Bu); ¹³C{¹H} NMR (C₆D₆) d 199.4 (CO), 93.0(CH_(diket)), 75.0 (CHMe₂), 71.4 (CHMe₂), 40.8 (CMe₃), 28.3 (CMe ₃),26.4 (CHMe ₂), 25.8 (CHMe ₂).

Example 3 Synthesis of Nb(OEt)₄(η²-thd)

The procedure of Example 1 is followed, using Nb(OEt)₅ as startingmaterial rather than the tantalum ethoxide. One equivalent of2,2,6,6-tetramethyl-3,5-heptanedione (Hthd) is added directly toNb(OEt)₅ in a Schlenk flask. The vessel is heated to about 65° C. undera slow nitrogen purge to a bubbler. After 2 hours the ethanol generatedis removed in vacuo to yield Nb(OEt)₄(η²-thd) in quantitative yield.

Example 4 Synthesis of Nb(OiPr)₄(η²-thd)

A nine-fold molar excess of isopropanol is added to Nb(OEt)₄(η²-thd).The resulting solution is heated at 60° C. for 45 min, following whichthe volatiles are removed in vacuo. The ligand exchange procedure isrepeated a second time to yield solid Nb(O-i-Pr)₄(η²-thd) inquantitative yield. The product is purified by sublimation at 100° C. at150 mtorr.

Example 5 Deposition of Niobia Film

Nb(O-i-Pr)₄(η²-thd) is used to deposit Nb₂O₅ (“niobia”) on a siliconwafer held at 400° C. in a CVD reactor. The Nb reagent is contained in avessel (“bubbler”) held at 185° C. and Ar gas is flowed through thevessel at 100 sccm. Pressure in the “bubbler” is controlled at 80 torrusing a manual throttle valve. Oxygen is flowed to the reactor through aseparate manifold at 300 sccm. Total pressure in the reactor is 1 torrand partial pressure of the Nb reagent in the reactor is 0.03 torr.Deposition rate is approximately 0.04 mm/minute.

Example 6 Deposition of Tantala Film

Ta(O-i-Pr)₄(thd) is used to deposit Ta₂O₅ (tantala) on a fused silica(glass) envelope of a high intensity lamp by chemical vapor deposition.The glass surface is held at 450° C. in a CVD reactor. TheTa(O-i-Pr)₄(thd) compound is dissolved in an organic solvent and thisliquid solution is pumped to a vaporization zone of the reactor held at200° C. where Ar carrier gas is also introduced at 100 sccm. At thevaporizer zone the solvent evaporates, the Ta compound sublimes and thegaseous reagents and Ar then flow to the chemical vapor depositionreactor. Oxygen is flowed to the reactor through a separate manifold at300 sccm. Total pressure in the reactor is 1 torr and the depositionrate is 0.065 mm/minute.

Example 7 Deposition of Nb:BST

Nb(O-i-Pr)₄(η²-thd) is used to deposit Ba_(1-x)Sr_(x)Ti_(1-y)Nb_(y)O₃(Nb:BST) on a platinum metal layer on a silicon wafer in a CVD reactor.The metal layer will act as a bottom electrode in a capacitor and theNb:BST film will have a high dielectric constant with dc low leakagecurrent density. The platinum surface is held at 650° C.Nb(O-i-Pr)₄(η²-thd) reagent is dissolved in an organic solvent alongwith Ba(thd)₂-tetraglyme, Sr(thd)₂-tetraglyme and Ti(OPr)₂(thd)₂, andthis liquid solution is pumped to a vaporization zone held at 220° C.where Ar carrier gas is also introduced at 600 sccm. The solution isstable and no detrimental levels of ligand exchange occurred between themetallorganic compounds in the liquid phase or gas phase. At thevaporization zone the solvent evaporates and the Bi, Sr, and Ticompounds sublime and pass into the vapor phase. The gaseous reagentsand Ar then flow to the CVD reactor. A mixture of oxygen and nitrousoxide is flowed to the reactor through a separate manifold at 300 sccmeach. Total pressure in the reactor is 0.700 torr and the (Nb:BST) isefficiently deposited.

Example 8 Deposition of Bi₂SrTa₂O₉

Ta(O-i-Pr)₄(thd) is used to deposit Bi₂SrTa₂O₉ on platinum metal layeron a silicon wafer in a CVD reactor. The Bi₂SrTa₂O₉ film will form aferroelectric capacitor with remanent polarization that can be switchedgreater than 10¹² times. The Bi₂SrTa₂O₉ is deposited at 650° C.Ta(O-i-Pr)₄(thd) is dissolved in an organic solvent along withtriphenylbismuth and Sr(thd)₂-tetraglyme and this liquid solution ispumped to a vaporization zone held at 200° C. where Ar carrier gas isalso introduced at 100 sccm. The solution is stable and no detrimentalligand exchange occurred between the metallorganic compounds in theliquid or gas phase. At the vaporization zone the solvent evaporates andthe Bi, Sr, Na compounds sublime. The gaseous reagents and Ar then flowto the chemical vapor deposition reactor. A mixture of oxygen andnitrous oxide is flowed to the reactor through a separate manifold at300 sccm each. Total pressure in the reactor is 2.1 torr and theBi₂SrTa₂O₉ is deposited at useful rates.

Example 9 Growth of GMR Oxide Films on LaAlO₃ (100), NdGaO₃ (110), andMgO (100) Substrates by CVD

La_(x)Ca_(1-x)MnO₃ films were grown on LaAlO₃ (100), NdGaO₃ (110), andMgO (100) substrates by CVD in the CVD system that is shownschematically in FIG. 1. Tris(tetramethylheptanedionato)lanthanum(La(thd)₃), bis(tetra-methylheptanedionato) calcium (Ca(thd)₂), andtris(tetramethylheptane-dionato)manganese (Mn(thd)₃), all of which werepurchased commercially (Strem Chemicals), were used as precursormaterials. These three organic compounds, in appropriate amounts, weremixed and dissolved in a single organic solution of 25:1 butylacetate:tetraglyme under an inert atmosphere. The concentrations ofLa(thd)₃, Ca(thd)₂ and Mn(thd)₃ in the solution were 0.033, 0.017, and0.05 moles/liter of solution, respectively. During deposition, thesolution was constantly injected into a vaporizer by a liquid pump andthe vapors were carried immediately into a chemical vapor depositionreactor by nitrogen gas. The films were deposited at a constant pressureof 1.5 Torr and at a substrate temperature ranging from 600° C. to 700°C. Both oxygen and nitrous oxide were used as oxidants.

The films were characterized and showed a high transition temperatureT_(c) in the as-deposited films, probably due to the higher oxygenpartial pressure in the CVD process. The highest T_(c) attained was300K. The peak value of resistivity r is observed to decrease from34mΩ-cm to 12 mΩ-cm in the film with T_(c)=300K. Post annealing of thesefilms in 1 atm of O₂ further reduced r and increased T_(c). The oxygencontent plays an important role in controlling the carrierconcentration. All of the films prepared at different substratetemperatures between 600 and 750° C. were highly (001) oriented. Thegrain size of films decreased as the substrate temperature decreasedwithout a degradation of crystallinity determined by XRD in thistemperature range. There was no correlation found between grain size andcusp temperature or magnetoresistance of the films. The preferredorientation of the films appear to affect on the temperature dependenceof resistivity as shown in the case of a (LaCa)MnO3 film deposited onMgO substrate. A lower ΔR/R_(H) effect of as-deposited (LaCa)MnO3 filmsby MOCVD than that of annealed (LaCa)MnO3 films prepared by laserdeposition is probably due to a relatively low resistivity of theseMOCVD films.

Example 10 Growth of Zirconium Titanate

A number of PZT runs were performed with the objectives of optimizingvaporizer conditions and achieving desired film stoichiometry, fromZr(thd)₄ and Ti(O-iPr)₄ source reagents. The CVD reactor was constructedto permit preheating of the carrier gas using heat tape around anin-line filter, and the delivery system for vaporization and transportof the source reagent vapor was arranged and constructed in accordancewith the disclosure of U.S. Pat. No. 5,204,314.

Initial experiments employed as the solvent a mixture of THF:tetraglymein the ratio of 9:1. It was found that the effect of carrier gas preheatwas minimal. Vaporizer temperature was a much stronger variable withincreased vaporization temperature giving somewhat more consistentvaporization as judged by monitoring the pressure of the vaporizerbehind the frit (vaporization element). Lower temperatures (T_(vap)=215°C.) resulted in more erratic vaporizer pressure. In addition, increasedrelative Zr content in the solution caused wide swings in vaporizerpressure as the run progressed, even at T_(vap)=230° C. (Total Zrcontent in all cases has been held at 0.15 to 0.145 moles/liter solutionto prevent delivery tube clogging which was experienced at higher Zrconcentrations.)

One variable studied in the test was the addition of isopropanol to thesolvent. In such modification, the solvent used wasTHF:isopropanol:tetraglyme in the ratio of 8:2:1. IPA affected theprocess remarkably favorably in respect of the desired film composition.Zr incorporation efficiency increased to the point where films ofZr_(x)Ti_(1-x)O₄ were produced. The deposition conditions were heldconstant during all of the experiments, evidencing the fact thattransport of Zr is significantly enhanced by the addition of IPA to theTHF/tetraglyme solvent. This suggested that ligand exchange may haveplayed a role, e.g., with the reactionZr(thd)₄-->Zr(OiPr)_(x)(thd)_(4-x), leading to more volatile species. Itwas also observed that the swings in vaporizer pressure decreased (atT_(vap)=230° C. and with 40 mm fits) with the modified solvent. Ligandexchange may also have led to the provision of all liquid precursors atthe vaporizer temperature rather than solid as is the case for Zr(thd)₄.

Example 11 Growth of BiSrTa

Transport experiments for Bi—Sr—Ta were conducted in a CVD reactor toroughly determine vaporizer operating conditions, following which two Tacompounds were evaluated. The first was Ta(OiPr)₄(thd), for which threevaporizer temperatures were investigated. The best condition was foundto be 200° C. A second Ta compound, Ta₂(OEt)₄(thd) also was tried underthe same transport conditions, as summarized in Table V below.

TABLE V Frit pore size 20 μm Carrier gas flow 450 sccm Ar (preheated)Precursors BiPh₃, Sr(thd)₂, and Ta(OiPr)₄(thd) or Ta(OEt)₄(thd) Solvent8:2:1 THF:isopropanol:tetraglyme Reagent solutionBi0.40M—Sr0.15M—Ta0.40M concentrations Delivery rate 0.1 ml/min Systembase pressure 2 torrTa(OiPr)₄(η²-thd)

The 180° C. experiment resulted in a steep rise in pressure behind thefrit, presumably due to unsublimed material (likely Sr(thd)₂) which wasconsistent with the fact that the pressure behind the frit recovered by93% to nearly its initial value in about 1.5 hours.

The 200° C. experiment had a steep initial pressure rise, followed bythe lowest steady-state rise of any of the conditions tried. Arelatively low pressure recovery after the experiment (29%) indicatedthat some decomposition of metalorganic material occurred at the frit.

The 220° C. experiment behaved similarly to the 200° C. experiment withtwo exceptions: the steady state rise was >2× higher and a steeppressure rise occurred at the end of the experiment (˜2 hours) which wasaccompanied by a clog in the delivery tube at the frit. The clogdisappeared as the vaporizer cooled overnight and a significant amount(about a 5 mm dia. lump) of white material was present on top of thefrit. This may have been due to the reagent being sucked into thevaporizer from the delivery tube (with some leakage through the 20 psicheck valve) from which the solvent had evaporated. An NMR analysis wasconducted on the material, and it showed BiPh₃ and Ta(OiPr)₄(thd)precursors in about their original ratios but no Sr(thd)₂.

The frit residue was analyzed qualitatively by x-ray fluorescence (XRF).The results showed that the amount of Bi and Ta left on the fritincreased with increasing vaporizer temperature, as expected.

Ta(OEt)₄(η²-thd)

This compound appeared fairly well behaved until near the end of thetransport experiment, where a significant rise in pressure behind thefrit occurred, accompanied by a clog in the delivery system. This clogdisappeared within minutes of shutting off the solution flow. Vaporizerpressure recovered by about 62% after the experiment.

Several films were deposited on Pt/Ta/SiO₂/Si during the transportexperiments. Deposition at 750° C. susceptor temperature resulted in afilm that was poorly crystallized. In contrast, films deposited at 800°C. showed strong XRD peaks. Interestingly, all films had a stripedappearance across the wafer indicating changing thickness. This may beattributable to a macroscopic manifestation of ledge motion duringgrowth of the compound which is known to be a layered structure. Fringeswere observed moving across the wafer at the early stages of growth.

Example 12 Growth of BaTiO₃ from Ti(OR)₂(thd)₂

A source reagent mixture of Ti(OR)₂(acac)₂ and Ba(thd)₂ in solventmedium was found to experience ligand exchange, resulting in mixedBa(β-diketonate)₂ species that display a reduced volatility. Use ofTi(OR)₂(thd)₂ in place of Ti(OR)₂(acac)₂ resulted in degenerate ligandexchange that was transparent to the vaporization and CVD depositionprocess.

Example 13 Growth of Bi₂SrTa₂O₉ Using Ta(OEt)₄(thd)

The combination of reagents Ta(OEt)₅ and Sr(thd)₂ also resulted inligand exchange when the ligands were dissolved in solvent medium, as inExample 12. By using Ta(OEt)₄(thd) the aforementioned exchange problemis alleviated in solution. This enables a reproducible transport and CVDprocess.

The Ta(OEt)₄(thd) and Sr(thd)₂ solution can be used for depositing SrTaOor Bi₂SrTa₂O₉ materials.

Example 14 Growth of BaTiO₃ or BST Using Ti(OR)₂(thd)₂

The source reagent combination of Ti(OR)₄ and Ba(thd)₂ can undergoligand exchange as described in Examples 12 and 13. Use of Ti(OR)₂(thd)₂as the Ti reagent alleviates the exchange problem in solution. Thelatter solution can be used for the formation of BaTiO or BaSrTiO films.

Example 15 Growth of PbTiO₃

The source reagent combination of Ti(OR)₄ and Pb(thd)₂ can also resultin ligand exchange in solution. Using Ti(OR)₂(thd)₂ eliminates theligand exchange with the Pb reagent. The latter solution is useful fordeposition of PbTiO₃ or PbZrTiO₃ (PZT) films.

Example 16 Growth of YBCO

Y(thd)₃, Ba(thd)₂, and Cu(thd)₂ were dissolved in an appropriate solventto enable the facile vaporization and gas-phase transport of theprecursors into the reaction zone. The volatility and transportcharacteristics of the reagents are primarily governed by the thdligands and the temperature of the heated vaporization zone of theliquid delivery system. These solutions can be used forY_(x)Ba_(y)Cu_(z)O film growth.

Example 17 Growth of YBCO

Various metal (β-diketonates) are dissolved in the desired solvent toprovide compatible solubilities. For example, Cu(thd)₂ or Cu(hfacac)₂reagents are used in tandem with the similar Y(thd)₃ or Y(hfacac)₃reagents, respectively, to realize comparable solubilities of widelydiffering metals.

Example 18 CVD of Aluminum—Addition of Solvent to Decrease PrecursorViscosity

An inert solvent is added to a “neat” liquid or reagent being used forfilm growth. Dimethyl aluminum hydride (dimer) is a viscous liquid thatyields high-purity aluminum films. Liquid delivery is facilitated bydilution in an inert organic solvent, such as hexane or toluene. Thedilute solution is easily transported to the vaporization zone fordeposition. Other organic solvents with a suitable boiling point can beused with equal success.

Example 19 Solvent System to Optimize Liquid Delivery of Reactants forCVD

A solvent is chosen, such that preferential boiling of the solvent doesnot occur without volatilization of the reagent. This allows maximumvolatilization of the reagent to be realized without detrimentalclogging of the vaporizer. For example, the use of atetrahydrofuran-isopropanol mixture is advantageous for the deliveryvaporization of Bi(Ph)₃ and Ta(OiPr)₄(thd).

Example 20 Use of Additive to Increase Reactant Solubility for LP CVD

Acetone, tetrahydrofuran, dimethoxyethane (DME) or dimethylformamide(DMF) are added to a solution containing Ba(thd)₂ to maximize itssolubility.

Example 21 Use of Polyethers to Improve Suitability for LP CVD

Various compositions were made up of reagent solutions, including:addition of 4-glyme to Ba(thd)₂; addition of polyamines for Ba(thd)₂;addition of polyether alcohols to enhance thermal stability of reagents;and addition of 18-crown-6 to enhance the thermal stability of thereagents.

Example 22 Use of Solvent to Lower Freezing Point of Low-Melting Solid

Ta(OEt)₅ has a melting point of ˜21° C. Liquid delivery of this materialrequires a lowering of the freezing point to maintain a liquid in thebubbler and throughout the process system. Lowering the freezing pointis achieved by addition of ethanol to the ‘neat’ Ta(OEt)₅ used to growTa₂O₅ films. The ethanol does not have a deterimental effect on thereagent, the liquid delivery or the reagent and/or the CVD growthprocess.

Example 23 Addition of Solvent to Depress Freezing Point of Low MeltingSolids

Ti(OiPr)₄, m.p. of 20° C., is mixed with i-PrOH to lower the meltingpoint. MgAl₂(OiPr)₈, m.p. 40° C., is mixed with iPrOH to lower themelting point. Ta(OEt)₄(thd), m.p.=26° C., is mixed with EtOH to lowerthe melting point.

Example 24 Liquid Delivery of Cu Reagents—Solvent Coordination forAltering Complex Properties

A solvent is chosen to maximize dissolution of a reagent based upon thesolubility of that precursor in a given solvent. However, the solventmay be chosen to provide a solvated complex that exhibits differentphysical properties after solvation. Cu(hfacac)₂ hydrate is exceedinglysoluble in alcoholic solvents because the water is displaced and thealcohol coordinates to the metal center. Isolation of the solvatedcomplex yields materials with different physical properties. Thus, thesolvent is chosen to alter the physical and chemical properties of thereagent being used for film growth.

Complex Tm (° C.) Tdec. (° C.) Cu(hfacac)₂(MeOH) 134-138 250Cu(hfacac)₂(EtOH) 103-104 250 Cu(hfacac)₂(iPrOH) 53-55 210

This same concept can be extended to a wide variety of other reagentswhich can be solvated to provide complexes of different physico-chemicalproperties for use in CVD. For example, tetrahydrofuran (THF) may beadded to a solution to increase the solubility of Cu(thd)₂ therein.

Example 25 Use of Additive to Increase Reactant Stability for LP CVD

Tetraglyme was added to Ba(thd)₂(tetraglyme) solution to enhance thermalstability of the reagent composition.

Example 26 Addition of Excess Lewis Base to Increase Reactant StabilityDuring LP CVD

Lewis base copper(I) β-diketonate complexes are useful for copper CVD.However, the Lewis base may be easily liberated from the moleculeresulting in pre-mature decomposition and clogging of the vaporizer. Tocombat this problem, excess Lewis base is added. Similarly, excess Lewisbase can be added to stop the formation of a less volatile dinuclearspecies and eliminate precipitation in the vaporizer. For example,liberation of 3-hexyne from 3-hexyne Cu(hfacac) leads to the formationof a dinuclear complex, 3-hexyne [Cu(hfacac)]₂, which is a solid at roomtemperature. The formation and precipitation of this dinuclear solid canbe controlled by forcing this equilibrium in the reverse direction.Thus, excess 3-hexyne not only enhances the thermal stability, buteliminates formation of a less volatile solid precipitate, which canlead to clogging and decomposition in the vaporizer.

Example 27 Addition of Polyether or Polyamine to Reduce Hydrolysis ofReactant During LP CVD

The coordination of H₂O to Ba(thd)₂ on thermal vaporization may bereduced or eliminated by coordinating a stronger Lewis Base to thebarium center.

Example 28 Formation of CuS-Based Films

A solution consisting of copper (II)bis(1,1,1,5,5,5-hexafluoro-2-thio-pentane-4-one) was dissolved in anorganic solvent containing n-butyl acetate and tetraglyme (25:1). Thesolution was delivered to a warm-walled reactor using a liquid deliverysystem and reacted with H₂S to produce a copper sulfide (CuS) basedfilm. This approach can be used to produce complex copper sulfides byco-reaction with a third reactant to produce films such as CuInS, CuGaSand CuSeS films.

Example 29 Formation of SrS Films in Presence of H₂S

A solution consisting of strontium (II)bis(2,2,6,6,-tetramethyl-3-thio-heptane-5-one) was dissolved in asolution of n-butyl acetate and tetraglyme (25:1). This solution wasdelivered, using a commercial liquid delivery system, to a CVD reactorand reacted with H₂S to produce high quality SrS films. These films canbe used as a white phosphor layer for electroluminescent displayapplications.

Example 30 Formation of SrS Films With Thiol-Containing Source Solution

In a modification to Example 29, a solution consisting of strontium (II)bis(2,2,6,6,-tetramethyl-3-thio-heptane-5-one) was dissolved in asolution of n-butyl acetate and tetraglyme (25:1). This solution alsocontained a sulfur source, such as t-butylthiol or cyclohexyl thiol andwas delivered (using a commercial liquid delivery system) to a CVDreactor to produce high quality SrS films. The incorporation of thethiol obviates the need for co-reaction with H₂S and therefore, is moredesirable for health, safety and environmental reasons; this willfacilitate manufacturing of SrS as a white phosphor layer forelectroluminescent display applications.

Example 31 Formation of SrS Films in Presence of H₂S with ButylAcetate/Tetrathiocyclodecane Solvent System

In a modification to Examples 29 and 30, a solution consisting ofstrontium (II) bis (2,2,6,6,-tetramethyl-3-thio-heptane-5-one) wasdissolved in a solution of n-butyl acetate and tetrathiocyclodecane.This solution was delivered (using a commercial liquid delivery system)to a CVD reactor and co-reacted with H₂S to produce high quality SrSfilms. These films can be used as a white phosphor layer forelectroluminescent display applications.

Example 32 Formation of Ce-Doped (Ca, Sr)Ga₂S₄ Films in Presence of H₂S

In a separate approach, multi-component phosphors, such as Ce doped(Ca,Sr)Ga₂S₄ can be deposited by liquid delivery of one or moresolutions containing the following co-reactants; Ca (II)bis(2,2,6,6,-tetramethyl-3-thioheptane-5-one), Sr (II)bis(2,2,6,6,-tetramethyl-3-thio-heptane-5-one), Ga (III) tris(2,2,6,6,-tetramethyl-3-thioheptane-5-one) and Ce (IV) tetrakis(2,2,6,6,-tetramethyl-3-thioheptane-5-one). These reactants aredissolved into n-butyl acetate and tetraglyme (25:1) and delivered tothe CVD reactor for Ce doped (Ca,Sr)Ga₂S₄ film growth with H₂S as thesulfur source. The concentrations of each component can be controlledvia the concentration of the individual components in solution or viamixing of individual solutions of the reactants. The resultingthiogallate film can be used for electroluminescent films in displayapplications.

Example 33 Formation of Ce-Doped (Ca, Sr)Ga₂S₄ Films WithThiol-Containing Solvent System

In a modification of Example 32, a Ce doped (Ca,Sr)Ga₂S₄ film can bedeposited by liquid delivery of one or more solutions containing thefollowing co-reactants; Ca (II) bis(2,2,6,6,-tetramethyl-3-thio-heptane-5-one), Sr (II)bis(2,2,6,6,-tetramethyl-3-thio-heptane-5-one), Ga (III) tris(2,2,6,6,-tetramethyl-3-thio-heptane-5-one) and Ce (IV) tetrakis(2,2,6,6,-tetramethyl-3-thio-heptane-5-one). These reactants aredissolved into n-butyl acetate, tetraglyme (25:1) and sulfur containingsource, such as t-butyl thiol or cyclohexyl thiol. The incorporation ofthe thiol obviates the need for co-reaction with H₂S and therefore, ismore desirable for manufacturing and environmental reasons.

Example 34 Formation of Ce-Doped (Ca, Sr)Ga₂S₄ Films WithThiol-Containing Solvent System and Deposition in the Presence ofHydrogen Sulfide Gas

In a modification of Examples 32 and 33, a Ce doped (Ca,Sr)Ga₂S₄ filmcan be deposited by liquid delivery of one or more solutions containingthe following co-reactants; Ca (II)bis(2,2,6,6,-tetramethyl-3-thioheptane-5-one), Sr (II)bis(2,2,6,6,-tetramethyl-3-thioheptane-5-one), Ga (III) tris(2,2,6,6,-tetramethyl-3-thioheptane-5-one) and Ce (IV) tetrakis(2,2,6,6,-tetramethyl-3-thioheptane-5-one). These reactants aredissolved into n-butyl acetate, tetrathiollcyclodecane and delivered tothe CVD reactor for Ce doped (Ca,Sr)Ga₂S₄ film growth with H₂S as thesulfur source. The concentrations of each component can be controlledvia the concentration of the individual components in solution or viamixing of individual solutions of the reactants. The resultingthiogallate film can be used for electroluminescent films in displayapplications.

Example 35 Formation of CuS Films, and Binary Metal Sulfide Films

A solution consisting of copper (II)bis(1,1,1,5,5,5-hexafluoro-2,4-pentanedionato) was dissolved in anorganic solvent containing i-propanol, tetrahydrofuranacetate andtetraglyme (2:8:1). The solution was delivered to a warm-walled reactorusing a liquid delivery system and reacted with H₂S to produce a coppersulfide based film. In a modification of this method, the sulfur sourceis t-butylthiol, octanethiol or cyclohexylthiol and is a component ofthe solution. This approach can be used to produce complex coppersulfides by co-reaction with a third reactant to produce films such asCuInS, CuGaS and CuSeS films for a variety of applications.

Example 36 Formation of CuS Films, and Binary Metal Sulfide Films

A solution consisting of copper (II)bis(1,1,1,5,5,5-hexafluoro-2-,4-pentanedione) was dissolved in anorganic solvent containing n-butyl acetate and tetraglyme (25:1). Thesolution was delivered to a warm-walled reactor using a liquid deliverysystem and reacted with H₂S to produce a copper sulfide (CuS) basedfilm. This approach can be used to produce complex copper sulfides byco-reaction with a third reactant to produce films such as CuInS, CuGaSand CuSeS films.

Example 37 Formation of SrS Films

A solution consisting of strontium (II)bis(2,2,6,6,-tetramethyl-3,5-heptanedione) was dissolved in a solutionof n-butyl acetate and tetraglyme (25:1). This solution was delivered,using a commercial liquid delivery system, to a CVD reactor and reactedwith H₂S to produce high quality SrS films. These films can be used as awhite phosphor layer for electroluminescent display applications.

Example 38 Formation of SrS Films

In a modification to Example 29, a solution consisting of strontium (II)bis(2,2,6,6,-tetramethyl-3,5-heptanedione) was dissolved in a solutionof n-butyl acetate and tetraglyme (25:1). This solution also contained asulfur source, such as t-butylthiol or cyclohexyl thiol and wasdelivered (using a commercial liquid delivery system) to a CVD reactorto produce high quality SrS films. The incorporation of the thiolobviates the need for co-reaction with H₂S and therefore, is moredesirable for health, safety and environmental reasons; this willfacilitate manufacturing of SrS as a white phosphor layer forelectroluminescent display applications.

Example 39 Formation of SrS Films

In a modification to Examples 29 and 30, a solution consisting ofstrontium (II) bis (2,2,6,6,-tetramethyl-3,5-heptanedione) was dissolvedin a solution of n-butyl acetate and tetrathiocyclodecane. This solutionwas delivered (using a commercial liquid delivery system) to a CVDreactor and co-reacted with H₂S to produce high quality SrS films. Thesefilms can be used as a white phosphor layer for electroluminescentdisplay applications.

Example 40 Formation of Ce-Doped (Ca, Sr)Ga₂S₄ Films in the Presence ofHydrogen Sulfide Gas

In a separate approach, multi-component phosphors, such as Ce doped(Ca,Sr)Ga₂S₄ can be deposited by liquid delivery of one or moresolutions containing the following co-reactants; Ca (II)bis(2,2,6,6,-tetramethyl-3,5-heptanedione), Sr (II)bis(2,2,6,6,-tetramethyl-3,5-heptanedione), Ga (III) tris(2,2,6,6,-tetramethyl-3,5-heptanedione) and Ce (IV) tetrakis(2,2,6,6,-tetramethyl-3,5-heptanedione). These reactants are dissolvedinto n-butyl acetate and tetraglyme (25:1) and delivered to the CVDreactor for Ce doped (Ca,Sr)Ga₂S₄ film growth with H₂S as the sulfursource. The concentrations of each component can be controlled via theconcentration of the individual components in solution or via mixing ofindividual solutions of the reactants. The resulting thiogallate filmcan be used for electroluminescent films in display applications.

Example 41 Formation of Ce-Doped (Ca, Sr)Ga₂S₄ Films WithThiol-Containing Solvent System

In a modification of Example 32, a Ce doped (Ca,Sr)Ga₂S₄ film can bedeposited by liquid delivery of one or more solutions containing thefollowing co-reactants; Ca (II) bis(2,2,6,6,-tetramethyl-3,5-heptanedione), Sr (II)bis(2,2,6,6,-tetramethyl-3,5-heptanedione), Ga (III) tris(2,2,6,6,-tetramethyl-3,5-heptanedione) and Ce (IV) tetrakis(2,2,6,6,-tetramethyl-3,5-heptane-dione). These reactants are dissolvedinto n-butyl acetate, tetraglyme (25:1) and sulfur containing source,such as t-butyl thiol, octylthiol or cyclohexyl thiol. The incorporationof the thiol obviates the need for co-reaction with H₂S and therefore,is more desirable for manufacturing and environmental reasons.

Example 42 Formation of Ce-Doped (Ca, Sr)Ga₂S₄ Films WithThiol-Containing Solvent System and Deposition in the Presence ofHydrogen Sulfide Gas

In a modification of Examples 32 and 33, a Ce doped (Ca,Sr)Ga₂S₄ filmcan be deposited by liquid delivery of one or more solutions containingthe following co-reactants; Ca (II)bis(2,2,6,6,-tetramethyl-3,5-heptanedione), Sr (II)bis(2,2,6,6,-tetramethyl-3,5-heptanedione), Ga (III) tris(2,2,6,6,-tetramethyl-3,5-heptanedione) and Ce (IV) tetrakis(2,2,6,6,-tetramethyl-3,5-heptane-dione). These reactants are dissolvedinto n-butyl acetate, tetrathiacyclodecane and delivered to the CVDreactor for Ce doped (Ca,Sr)Ga₂S₄ film growth with H₂S as the sulfursource. The concentrations of each component can be controlled via theconcentration of the individual components in solution or via mixing ofindividual solutions of the reactants. The resulting thiogallate filmcan be used for electroluminescent films in display applications.

Example 43 Formation of CuS Films With Thiol-Containing Solvent Systemand Deposition in the Presence of Hydrogen Sulfide Gas, and Productionof Films of Binary Metal Sulfide Films

A solution consisting of copper (II)bis(1,1,1,5,5,5-hexafluoro-2,4-pentanedionato) in an organic solventcontaining i-propanol, tetrahydrofuranacetate and tetraglyme (2:8:1).The solution was delivered to a warm-walled reactor using a liquiddelivery system and reacted with H₂S to produce a copper sulfide basedfilm. In a modification of this method, the sulfur source ist-butylthiol, octanethiol or cyclohexylthiol and is a component of thesolution. This approach can be used to produce complex copper sulfidesby co-reaction with a third reactant to produce films such as CuInS,CuGaS and CuSeS films for a variety of applications.

Example 44 Formation of TiS₂ Films With Thiol-Containing Solvent Systemor Deposition in the Presence of Hydrogen Sulfide Gas

A solution consisting of titanium (III) tris(1,1,1,5,5,5-hexafluoro-2,4-pentanedionato) dissolved in an organicsolvent was delivered to a warm walled CVD reactor using a liquiddelivery system. The precursor was reacted with H₂S to deposit yellowfilms of TiS₂ as a lubricating layer onto metal parts. The process maybe varied by using organic thiols in the solution and thus, obviates theneed for H₂S co-reactant. This latter process is desirable for health,safety and environmental reasons.

Example 45 Formation of TiS₂ Films With Thiol-Containing Solvent Systemor Deposition in the Presence of Hydrogen Sulfide Gas

A solution consisting of titanium (III) tris(2,2,6,6-tetramethyl-3,5-heptanedionato) dissolved in n-butylacetate andwas delivered to a warm walled CVD reactor using a liquid deliverysystem. The precursor was reacted with H₂S to deposit yellow films ofTiS₂ as a lubricating layer onto metal parts. The process may bemodified by using organic thiols, such as t-butyl thiol, octylthiol andcyclohexylthiol, in the solution and thus, obviates the need forco-reactanting with H₂S. This latter process is desirable for health,safety and environmental reasons and enables full scale manufacturing tobe safely realized.

Example 46 Formation of MoS₂ Films With Thiol-Containing Solvent Systemor Deposition in the Presence of Hydrogen Sulfide Gas

A solution consisting of molybdenum (III) tris(1,1,1,5,5,5-hexafluoro-2,4-pentanedionato) dissolved in n-butylacetateand was delivered to a warm walled CVD reactor using a liquid deliverysystem. The precursor was reacted with H₂S to deposit yellow films ofMoS₂ as a lubricating layer onto metal parts. The process may be variedby using organic thiols in the solution and thus, obviates the need forH₂S co-reactant. This latter process is desirable for health, safety andenvironmental reasons.

Example 47 Formation of MoS₂ Films With Thiol-Containing Solvent Systemor Deposition in the Presence of Hydrogen Sulfide Gas

A solution consisting of molybdenum (III) tris(2,2,6,6-tetramethyl-3,5-heptanedionato) dissolved in n-butyl acetateand was delivered to a warm walled CVD reactor using a liquid deliverysystem. The precursor was reacted with H₂S to deposit films of MoS₂ as alubricating layer onto metal parts. The process may be varied by usingorganic thiols in the solution and thus, obviates the need for H₂Sco-reactant. This latter process is desirable for health, safety andenvironmental reasons.

While the invention has been described herein with reference to specificembodiments, features and aspects, it will be recognized that theinvention is not thus limited, but rather extends in utility to othermodifications, variations, applications, and embodiments, andaccordingly all such other modifications, variations, applications, andembodiments are to be regarded as being within the spirit and scope ofthe invention.

1. A β-diketonate alkoxide metal compound including a metal M selectedfrom the group consisting of Mg, Ca, Sr, Ba, Sc, Y, La, Ce, Ti, Zr, Hf,Pr, V, Nb, Ta, 2Nd, Cr, W, Pm, Mn, Re, Sm, Fe, Ru, Eu, Co, Rh, Ir, Gd,Ni, Tb, Cu, Dy, Ho, Al, Tl, Er, Sn, Pb, Tm, Bi, Lu, Th, Pd, Pt, Ga, In,Au, Ag, Li, Na, K, Rb, Cs, Mo, and Yb, wherein the metal is complexed to(i) at least one butoxy or isopropoxy ligand and (ii) at least onetetramethylheptanedionate ligand.
 2. The β-diketonate alkoxide metalcompound of claim 1, of the formulaM(OR)₂(thd)₂ wherein OR=isopropoxy and thd=tetramethylheptanedionate. 3.The β-diketonate alkoxide metal compound of claim 2, wherein M=titaniumor zirconium.
 4. The β-diketonate alkoxide metal compound of claim 1,comprisingZr(OiPr)₂(thd)₂ wherein OiPr=isopropoxy.
 5. The β-diketonate alkoxidemetal compound of claim 1, comprisingZr(OiPr)(thd)₃ wherein OiPr=isopropoxy.
 6. The β-diketonate alkoxidemetal compound of claim 1 in a solvent medium comprising a solventspecies selected from among glymes, aliphatic hydrocarbons, aromatichydrocarbons, ethers, esters, nitriles, and alcohols.
 7. Theβ-diketonate alkoxide metal compound of claim 6, wherein the solventmedium comprises a solvent species selected from among tetrahydrofuran,tetraglyme, butyl acetate, isopropanol, ethanol, tetrathiocyclodecane,and tetrahydrofuranecetate.
 8. A zirconium precursor compositioncomprising a zirconium central atom coordinated to at least onetetramethylheptanedionate ligand.
 9. The zirconium precursor compositionof claim 7, of the formula Zr(thd)₄ whereinthd=tetramethylheptanedionate.
 10. A zirconium precursor compositioncomprising a zirconium precursor compound including a zirconium centralatom coordinated to at least one isopropoxy ligand and wherein thezirconium precursor compound is associated with isopropanol.
 11. A leadprecursor composition comprising Pb(thd)₂ whereinthd=tetramethylheptanedionate.
 12. A process for forming a zirconium-and titanium-containing film, comprising conducting chemical vapordeposition using a zirconium precursor composition includingisopropanol.
 13. The process of claim 12, wherein the zirconiumprecursor composition comprises a zirconium precursor in which azirconium central atom is coordinated to isopropoxy and/ortetramethylheptanedionate ligands.
 14. The process of claim 12, whereinthe zirconium precursor comprises Zr(thd)₄.
 15. The process of claim 12,wherein the zirconium central atom in the zirconium precursor iscoordinated to isopropoxy and tetramethylheptanedionate ligands.
 16. Theprocess of claim 12, wherein said film comprises a lead zirconiumtitanate film.
 17. A metalorganic complex composition comprising one ormore metal central atoms coordinated to one or more coordinatingmonodentate or multidentate organic ligands, and complexed with one ormore complexing monodentate or multidentate ligands containing one ormore atoms independently selected from the group consisting of atoms ofthe elements C, N, H, S, O and F; wherein said one or more coordinatingmonodentate or multidentate ligands of the metalorganic complex comprisea ligand selected from the group consisting of beta-ketoiminates, andbeta-diiminates, and wherein the one or more metal central atoms areselected from the group consisting of Cu, Ba, Sr, La, Nd, Ce, Pr, Sm,Eu, Th, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Bi, Tl, Y, Pb, Ni, Pd, Pt, Al,Ga, In, Ag, Au, Co, Rh, Ir, Fe, Ru, Sn, Li, Na, K, Rb, Cs, Ca, Mg, Hf,V, Ta, Cr, Mo, Ti, Zr, Nb, and W, with the proviso that twoβ-ketoiminate ligands are not the only ligands coordinated to the one ormore metal central atoms, and with the proviso that when alkoxy andβ-ketoiminate are the only ligands coordinated to the one or more metalcentral atoms, then H is not a substituent of the keto carbon of theβ-ketoiminate ligand.
 18. A source reagent composition, selected fromthe group consisting of: (a) compositions comprising La(thd)₃: (i) in asolvent medium and/or (ii) coordinated to a coordination species to forma lanthanum-containing complex; and (b) compositions comprisingHf(iOPr)₂(thd)₂.
 19. The source reagent composition of claim 18,comprising La(thd)₃ in a solvent medium comprising tetraglyme.
 20. Thesource reagent composition of claim 18, comprising La(thd)₃ in a solventmedium comprising octane.
 21. The source reagent composition of claim18, comprising La(thd)₃ in a solvent medium comprising tetrahydrofuran.22. The source reagent composition of claim 18, comprising La(thd)₃coordinated to tetraglyme.
 23. The source reagent composition of claim18, comprising Hf(iOPr)₂(thd)₂. in a solvent medium comprising octane.